Lyotropic Liquid Crystal to Soft Mesocrystal Transformation in Hydrated Salt–Surfactant Mixtures

Hydrated CaCl₂, LiI, and MgCl₂ salts induce self‐assembly in nonionic surfactants (such as C₁₂H₂₅(OCH₂CH₂)₁₀OH) to form lyotropic liquid‐crystalline (LLC) mesophases that undergo a phase transition to a new type of soft mesocrystal (SMC) under ambient conditions. The SMC samples can be obtained by aging the LLC samples, which were prepared as thin films by spin‐coating, dip‐coating, or drop‐casting of a clear homogenized solution of water, salt, and surfactant over a substrate surface. The LLC mesophase exists up to a salt/surfactant mole ratio of 8, 10, and 4 (corresponding to 59, 68, and 40 wt % salt/surfactant) in the CaCl₂, LiI, and MgCl₂ mesophases, respectively. The SMC phase can transform back to a LLC mesophase at a higher relative humidity. The phase transformations have been monitored using powder X‐ray diffraction (PXRD), polarized optical microscopy (POM), and FTIR techniques. The LLC mesophases only diffract at small angles, but the SMCs diffract at both small and wide angles. The broad surfactant features in the FTIR spectra of the LLC mesophases become sharp and well resolved upon SMC formation. The unit cell of the mesophases expands upon SMC transformation, in which the expansion is largest in the MgCl₂ and smallest in the CaCl₂ systems. The POM images of the SMCs display birefringent textures with well‐defined edges, similar to crystals. However, the surface of the crystals is highly patterned, like buckling patterns, which indicates that these crystals are quite soft. This unusual phase behavior could be beneficial in designing new soft materials in the fields of phase‐changing materials and mesostructured materials, and it demonstrates the richness of the phase behavior in the salt–surfactant mesophases.     

Ultrasound‐Assisted Construction of Halogen‐Bonded Nanosized Cocrystals That Exhibit Thermosensitive Luminescence

Multi‐component organic nanocrystals that are comprised of two or more supramolecular building blocks can be used to extend the design and assembly scope of solid molecular materials. Herein, we report the use of ultrasonication to prepare halogen‐bonded stilbene‐based nano‐cocrystals that exhibit different photoemission properties, including one‐ and two‐phonon emission and fluorescence lifetimes, relative to those of macrodimensional crystals. The structural transformation from nano‐cocrystals into nanocrystals upon heating results in a luminescence red‐shift from greenish blue to yellow. The temperature‐dependent ratiometric luminescence may allow such nano‐cocrystals to be used as fluorescent sensors and thermosensitive materials.     

The uranium recovery from aqueous solutions using amidoxime modified cellulose derivatives. IV. Recovery of uranium by amidoximated hydroxypropyl methylcellulose

Amidoxime modified hydroxypropyl methylcellulose (HPMC) films (HPMC-g-AO) were used for the recovery of uranium from aqueous solutions by a complexation process. The adsorption experiments were carried out by immersion of a certain amount of films in UO₂ ²⁺ solutions (resultant pH 4.1) ranging in concentration from 100 to 1,000 ppm. The effect of temperature (25–50 °C) on the adsorption capacity of HPMC-g-AO was investigated at the optimized time. The adsorption kinetics and the thermodynamics as well as the adsorption capacity of HPMC-g-AO films were investigated. The adsorption capacity was found as 765 mg UO₂ ²⁺/g dry film. The kinetic and the thermodynamic parameters (i.e. activation energy, enthalpy, entropy and Gibbs free energy) for the interaction of UO₂ ²⁺ with HPMC-g-AO were calculated based on known basic relations. The results showed that adsorption occurred through strong electrostatic interactions with an enthalpy of ?36.5 kJ/mol. The desorption of UO₂ ²⁺ were investigated using different desorption agents such as EDTA, HCl, NaHCO₃, and NaOH. After the 2 weeks treatment period, the highest desorption yield were found as 23 % with NaHCO₃.     

Clean and reactive nanostructured cellulose surface

A simple, solvent-free and low cost method to activate the surface of nanofibrillated cellulose films for further functionalization is presented. The method is based on the oxidative properties of UV radiation and ozone, to effectively remove contaminants from nanocellulosic surface, which remains clean and reactive for at least a week. The efficiency of the method is demonstrated by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. In clear contrast to previous results on nanoscaled cellulose the relative atomic concentration of non-cellulosic carbon atoms was only 4 %, and water completely wetted the surface within seconds. After activation, neither chemical degradation nor morphological changes on cellulose were observed. This surface activation is essential for further functionalization of the film in dry state or nonpolar media. The surface activation was confirmed by silylation and a four times higher degree of substitution was achieved on the activated sample compared to non-activated reference film, as monitored with XPS.     

Consequences of weak Allee effect on prey in the May–Holling–Tanner predator–prey model

In this work, a modified Holling–Tanner predator–prey model is analyzed, considering important aspects describing the interaction such as the predator growth function is of a logistic type; a weak Allee effect acting in the prey growth function, and the functional response is of hyperbolic type. Making a change of variables and time rescaling, we obtain a polynomial differential equations system topologically equivalent to the original one in which the non‐hyperbolic equilibrium point (0,0) is an attractor for all parameter values. An important consequence of this property is the existence of a separatrix curve dividing the behavior of trajectories in the phase plane, and the system exhibits the bistability phenomenon, because the trajectories can have different ω ? limit sets; as example, the origin (0,0) or a stable limit cycle surrounding an unstable positive equilibrium point. We show that, under certain parameter conditions, a positive equilibrium may undergo saddle‐node, Hopf, and Bogdanov–Takens bifurcations; the existence of a homoclinic curve on the phase plane is also proved, which breaks in an unstable limit cycle. Some simulations to reinforce our results are also shown. Copyright © 2015 John Wiley & Sons, Ltd.     

Zethrene and Dibenzozethrene: Masked Biradical Molecules?

The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature ¹H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σ_max=4323 GM at 530 nm].     

Synthesis of 6-aryl- and 5-aroylcomanic acids from 5-aroyl-2-carbethoxy-4-pyrones via a deformylative rearrangement and ring-opening/ring-closure sequence

The reaction of 1-aryl-2-(dimethylaminomethylene)butane-1,3-diones with diethyl oxalate in the presence of sodium hydride in THF gave ethyl 5-aroyl-4-oxo-4H-pyran-2-carboxylates, from which 4-oxo-6-aryl-4H-pyran-2-carboxylic acids (6-arylcomanic acids) were obtained in high yields via acid-catalyzed deformylative rearrangement. 5-Aroyl-4-oxo-4H-pyran-2-carboxylic acids (5-aroylcomanic acids) were prepared via а ring-opening/ring-closure sequence by the reaction of 5-aroyl-2-carbethoxy-4-pyrones with piperidine and subsequent basic hydrolysis and acidification.     

Metallo Phthalocyanines bearing 2‐Isopropyl‐6‐methylpyrimidin‐4‐yloxy Substituents: Synthesis,Characterization, Aggregation Behavior,Antioxidant and Antibacterial Activity,and Electronic Properties

A novel phthalonitrile derivative bearing 2‐isopropyl‐6‐methylpyrimidin‐4‐yloxy substituents at peripheral positions was synthesized by a nucleophilic substitution reaction. Metallophthalocyanines were obtained from the reaction of the novel phthalonitrile with metal Zn, Cu, Co, and Ni salts. The characterization of the compounds was performed using elemental analysis as well as UV/Vis, FT‐IR, and ¹H‐NMR spectroscopy. The aggregation behaviors of phthalocyanine complexes were also investigated. These metallophthalocyanines do not show any aggregation behavior between 10^–4–10^–6 M concentration range in THF. The antioxidant activities of the synthesized compounds were evaluated using three different tests: 2, 2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical scavenging, metal chelating activity, and reducing power assays. All the compounds exhibited various antioxidant activities. In addition, antimicrobial activity of the compounds was tested over four gram positive and two gram negative bacteria. Moreover, the ground‐state geometries of the complexes were optimized using density functional theory (DFT) methods at B3LYP/6‐31G(d, p) level in order to obtain information about the 3D arrangements and electronic structure.