Calculation of the diamagnetic shielding of the nuclei by the point-charge approximation

It is shown that the diamagnetic shielding of the nuclei can be calculated to a good accuracy by using point-charge approximation. Very good results were obtained by the semiempirical SCC-MO method employing Clementi-Raimondi AO basis set.     

Size Effects of the Anions in the Ionothermal Synthesis of Carbon Nitride Materials

Semiconducting carbon nitride polymers are used in metal-free photocatalysts and in opto-electronic devices. Conventionally, they are obtained using thermal and ionothermal syntheses in inscrutable, closed systems and therefore, their condensation behavior is poorly understood. Here, the synthetic protocols and properties are compared for two types of carbon nitride materials – 2D layered poly(triazine imide) (PTI) and hydrogen-bonded melem hydrate – obtained from three low-melting salt eutectics taken from the systematic series of the alkali metal halides: LiCl/KCl, LiBr/KBr, and LiI/KI. The size of the anion plays a significant role in the formation process of the condensed carbon nitride polymers, and it suggests a strong templating effect. The smaller anions (chloride and bromide) become incorporated into triazine (C₃N₃)-based PTI frameworks. The larger iodide does not stabilize the formation of a triazine-based polymer, but instead it leads to the formation of the heptazine (C₆N₇)-based hydrogen-bonded melem hydrate as the main crystalline phase. Melem hydrate, obtained as single-crystalline powders, was compared with PTI in photocatalytic hydrogen evolution from water and in an OLED device. Further, the emergence of each carbon nitride species from its corresponding salt eutectic was rationalized via density functional theory calculations. This study highlights the possibilities to further tailor the properties of eutectic salt melts for ionothermal synthesis of organic functional materials.     

Impact of random-field-type disorder on nematic liquid crystalline structures

The European Physical Journal E - In the nanoscale regime, flow behaviors for liquids show qualitative deviations from bulk expectations. In this work, we reveal by molecular dynamics simulations...     

π-Annulation reactions of 4-thiazolidinone enaminones in the synthesis of fused bi- and tri-cyclic compounds

The α-C position in 4-oxo thiazolidinones functions as one of the three possible nucleophilic sites in these molecules. We used the inherent reactivity of α-C of the exocyclic double bond (a so called push pull system) to obtain bicyclic fused thiazolidinones via π-annulation cyclization. Appropriate reaction conditions to selectively activate this position and secondary nitrogen towards N,π-annulation were found. Furthermore, the intramolecular vinylogous iminium ion 6-exo-trig cyclization was used to access fused bicyclic precursors for the π-annulation in order to obtain the novel tricyclic structures stereoselectively.     

Several classes of integrable nonlinear ordinary differential equations (I) first-order equations

In this paper we give some results of integrability and several classes of integrable equations of first-order nonlinear ordinary differential equations. Many known results of integrability and integrable equations are special cases of them. They may be applied in physics and mechanics, and to derive soliton equations and find soliton solutions.     

Reduced coupled flapping wing-fluid computational model with unsteady vortex wake

Insect flight research is propelled by their unmatched flight capabilities. However, complex underlying aerodynamic phenomena make computational modeling of insect-type flapping flight a challenging task, limiting our ability in understanding insect flight and producing aerial vehicles exploiting same aerodynamic phenomena. To this end, novel mid-fidelity approach to modeling insect-type flapping vehicles is proposed. The approach is computationally efficient enough to be used within optimal design and optimal control loops, while not requiring experimental data for fitting model parameters, as opposed to widely used quasi-steady aerodynamic models. The proposed algorithm is based on Helmholtz–Hodge decomposition of fluid velocity into curl-free and divergence-free parts. Curl-free flow is used to accurately model added inertia effects (in almost exact manner), while expressing system dynamics by using wing variables only, after employing symplectic reduction of the coupled wing-fluid system at zero level of vorticity (thus reducing out fluid variables in the process). To this end, all terms in the coupled body-fluid system equations of motion are taken into account, including often neglected terms related to the changing nature of the added inertia matrix (opposed to the constant nature of rigid body mass and inertia matrix). On the other hand—in order to model flapping wing system vorticity effects—divergence-free part of the flow is modeled by a wake of point vortices shed from both leading (characteristic for insect flight) and trailing wing edges. The approach is evaluated for a numerical case involving fruit fly hovering, while quasi-steady aerodynamic model is used as benchmark tool with experimentally validated parameters for the selected test case. The results indicate that the proposed approach is capable of mid-fidelity accurate calculation of aerodynamic loads on the insect-type flapping wings.

     

The effect of magnetic nanoparticles upon the smectic-A to smectic-C* phase transition

We report on wide-angle X-ray scattering measurements along the smectic-A to chiral ferroelectric smectic-C* phase transition of the liquid crystal SCE9 and its mixture with maghemite magnetic nanoparticles of typical dimension 20 nm. The temperature profiles of the tilt angle are fitted by an extended mean-field model. Neither pre-transitional order effects nor variations in the SmA layer thickness are observed, indicating a rather negligible influence of these nanoparticles upon the molecular orientation at the smectic-A to smectic-C* phase transition of SCE9. These results are very different from what was observed for smaller CdSe nanoparticles (3.5 nm) where both a dilation of the smectic layers in the SmA phase and a crossover behaviour for the smectic-A to smectic-C* transition away from tricriticality have been observed for analogous concentrations.     

Effects of poly (ethylene glycol) chains conformational transition on the properties of mixed DMPC/DMPE-PEG thin liquid films and monolayers

Foam thin liquid films (TLF) and monolayers at the air–water interface formed by DMPC mixed with DMPE-bonded poly (ethylene glycol)s (DMPE-PEG₅₅₀, DMPE-PEG₂₀₀₀ and DMPE-PEG₅₀₀₀) were obtained. The influence of both (i) PEG chain size (evaluated in terms of Mw) and mushroom-to-brush conformational transition and (ii) of the liposome/micelle ratio in the film-forming dispersions, on the interfacial properties of mixed DMPC/DMPE-PEG films was compared.

Foam film studies demonstrated that DMPE-PEG addition to foam TLFs caused (i) delayed kinetics of film thinning and black spot expansion and (ii) film stabilization. At the mushroom-to-brush transition, due to steric repulsion increased DMPE-PEG films thickness reached 25 nm while pure DMPC films were only 8 nm thick Newton black films. It was possible to differentiate DMPE-PEG_2000/5000 from DMPE-PEG₅₅₀ by the ability to change foam TLF formation mechanism, which could be of great importance for “stealth” liposome design.

Monolayer studies showed improved formation kinetics and equilibrium surface tension decrease for DMPE-PEG monolayers compared with DMPC pure films.

SEM observations revealed “smoothing” and “sealing” of the defects in the solid-supported layer surface by DMPE-PEGs adsorption, which could explain DMPE-PEGs ability to stabilize TLFs and to decrease monolayer surface tension.

All effects in monolayers, foam TLFs and solid-supported layers increased with the increase of PEG Mw and DMPE-PEG concentration. However, at the critical DMPE-PEG concentration (where mushroom-to-brush conformational transition occurred) maximal magnitude of the effects was reached, which only slightly changed at further DMPE-PEG content and micelle/liposome ratio increase.     

Criticality controlled by cross-linking density in liquid single-crystal elastomers

A high-resolution calorimetry and deuteron-nuclear magnetic resonance study of a paranematic-nematic phase transition was performed on liquid single-crystal elastomers. We show that density variations of both rodlike and pointlike cross-links strongly affect the mean value and the dispersion of local mechanical fields. The system exhibits an inherent weakly disordered orientational state composed of regions with the temperature profile of the nematic order parameter ranging from first order to supercritical. On increasing the cross-linking density the predominantly first order thermodynamic response transforms into a predominantly supercritical one.