A Coordination-Chemical Basis for the Biological Function of the Phytochelatins

To fix toxic heavy-metal ions , plants synthesize the ligands (γ-Glu-Cys)_n-Gly (PC_n), whose simplest representative is the pentapeptide PC₂. The knowledge of the composition and stabilities of the cadmium complexes of PC₂ allow a better understanding of biological processes like the one outlined.     

A conjugation polyimine vitrimer: Fabrication and performance

Although polyimine vitrimers are a promising and invaluable class of self-healing materials owing to their great maneuverability and fast exchange of crosslinks without catalysts, it remains a challenge to improve the mechanical properties and thermal stability of the material by simply designing their internal structures. Herein, we report a conjugation polyimine vitrimer, which was prepared by polycondensation of terephthaldehyde, m-xylylene diamine and tris (2-aminoethyl) amine as crosslinker. The incorporation of m-xylylene diamine endows the materials with an expanded conjugation structure, which greatly improves its mechanical properties and thermal stabilities. On the other hand, m-xylylene diamine is less toxic and irritant than the linear aliphatic ones usually used, which makes the reactions more environment-friendly. Results show that these materials have excellent mechanical properties and thermal stability, perform good flexibilities after immersed in water and show very short relaxation times at elevated temperatures. In addition, especially, they exhibit good self-healing efficiency under the condition of heat, water and amine solvents without the need for any catalyst. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2531–2538     

Electronic and magnetic properties of small RhnCa (n = 1–9) clusters: A DFT study

The equilibrium geometries, relative stabilities, electronic and magnetic properties of small Rh_nCa (n = 1–9) clusters have been investigated by DFT calculations. The obtained results show that the three‐dimensional geometries are adopted for the lowest‐energy Rh_nCa clusters, and the doped Ca atom prefers locating on the surface of the cluster. Based on the analysis of the second‐order difference of energies, fragmentation energies and the HOMO‐LUMO energy gaps, we identify that the Rh₄Ca, Rh₆Ca, and Rh₈Ca clusters are relatively more stable than their neighboring clusters, and the doping of Ca enhances the chemical reactivity of the pure Rh_n clusters, suggesting that the Rh_nCa clusters can be used as nanocatalysts in many catalytic reactions. The magnetic moment for these clusters is mostly localized on the Rh atoms, and the doping Ca atom has no effect on the total magnetic moment of Rh_nCa clusters. The partial density of states, VIP, VEA, and η of these clusters in their ground‐state structures were also calculated and discussed. © 2015 Wiley Periodicals, Inc.     

Design and Selection of High Energy Materials based on 4,8-Dihydrodifurazano[3,4-b,e]pyrazine

In order to search for high energy density materials, various 4,8-dihydrodifurazano[3,4-b,e]pyrazine based energetic materials were designed. Density functional theory was employed to investigate the relationships between the structures and properties. The calculated results indicated that the properties of these designed compounds were influenced by the energetic groups and heterocyclic substituents. The -N\begin{document}$ _3 $\end{document} energetic group was found to be the most effective substituent to improve the heats of formation of the designed compounds while the tetrazole ring/-C(NO\begin{document}$ _2 $\end{document})\begin{document}$ _3 $\end{document} group contributed much to the values of detonation properties. The analysis of bond orders and bond dissociation energies showed that the addition of -NHNH\begin{document}$ _2 $\end{document}, -NHNO\begin{document}$ _2 $\end{document}, -CH(NO\begin{document}$ _2 $\end{document})\begin{document}$ _3 $\end{document} and -C(NO\begin{document}$ _2 $\end{document})\begin{document}$ _3 $\end{document} groups would decrease the bond dissociation energies remarkably. Compounds A8, B8, C8, D8, E8, and F8 were finally screened as the potential candidates for high energy density materials since these compounds possess excellent detonation properties and acceptable thermal stabilities. Additionally, the electronic structures of the screened compounds were calculated.     

Asymptotically almost periodic solutions of nonlinear Volterra difference equations with unbounded delay

The existence of almost periodic solutions of nonlinear Volterra difference equations with unbounded delay is obtained by using uniform stability properties of a bounded solution. An example is also given to illustrate obtained results.     

Theoretical study on structures and stabilities of [H,Ge,C,N

Theoretical investigations are performed for the first time on the simplest hydrogenated germanium cyanide [H,Ge,C,N], whose analogs [H,C(2),N] and [H,Si,C,N] have been detected in space and laboratory, respectively. The detailed potential energy surfaces in both singlet and triplet states are constructed at the CCSD(T)/6-311+G(3df,2p)//B3LYP/6-31G(d)+ZPVE level, including 18 minimum isomers and 26 interconversion transition states. The former three low-lying and kinetically stabilized isomers are HGeCN (1)1 (0.0 kcal/mol), HGeNC (1)2 (5.1 kcal/mol), and cyclic cCHNGe(1)7 (11.1 kcal/mol). In addition, five isomers HCNGe (1)3 (33.8), HNCGe (1)5 (29.8), cNHCGe (1)8 (37.9), HGeCN (3)1 (30.1), and HNCGe (3)5 (26.5) each have considerable barriers, despite their high energies. Future laboratory characterization and astrophysical detection of the eight [H,Ge,C,N] isomers, especially the former three low-lying species (1)1, (1)2, and (1)7, are highly recommended. The accurate spectroscopic data at the QCISD/6-311G(d,p) level are provided. For some species, the CBS-QB3 calculations are also performed. Wherever possible, comparisons with the analogous [H,C(2),N] and [H,Si,C,N] are made on the structural, energetic, and bonding properties.     

Relationship between phase structure and electrical properties of (K0.5Na0.5)NbO3-LiTaO3 lead-free ceramics

Lead-free piezoelectric ceramics of (1−x)K_0.5Na_0.5NbO₃-xLiTaO₃ (KNN-LT) system have been investigated in this work. X-ray diffraction, Raman spectra measurements, DSC (Differential Scanning Calorimetric), and dielectric constant versus temperature provide direct evidence that the phase transition temperature between tetragonal and orthorhombic shift to lower temperature with the increasing of LT content. The KNN-0.05LT ceramics exhibit the highest high-field d₃₃ up to 220 pm/V. At the same time, we also investigated the relationship between phase structure and electric properties, showing that the orthorhombic phase presents better piezoelectric temperature stabilities than the tetragonal phase. The result may provide a new way for KNN-based lead-free ceramics.     

On stationary convection and oscillatory motions in ferromagnetic convection in a ferrofluid layer

It is shown analytically that the ‘principle of the exchange of stabilities’ (PES), in general, is not valid in ferromagnetic convection in a ferrofluid layer, for the case of free boundaries and hence a sufficient condition is derived for the validity of the PES. Upper bounds for the complex growth rate are then obtained. It is proved that the complex growth rate σ=σ_r+iσ_i (where σ_r and σ_i are, respectively, the real and imaginary parts of σ) of an arbitrary oscillatory motion of growing amplitude, in ferromagnetic convection in a ferrofluid layer, for the case of free boundaries lies inside a semicircle in the right half of the σ_rσ_i-plane whose center is at the origin and ²(radius)=RM₁/P_r, where R is the Rayleigh number,M₁ is the magnetic number and P_r is the Prandtl number. Further, bounds for the case of rigid ferromagnetic boundaries are also derived separately.     

Quantum Chemical Study of the Preferred Conformations,Molecular Geometries,and Relative Thermodynamic Stabilities of 2-Substituted 4-Methylene-1,3-Dioxolanes and 4-Methyl-1,3-Dioxoles

The preferred conformations, molecular geometries, and relative stabilities of carbon–carbon double-bond exo–endo isomeric 2-substituted 4-methylene-1,3-dioxolanes (a) and 4-methyl-1,3-dioxoles (b) have been studied by DFT calculations at the B3LYP/6-31G* level of theory. The main interest of this work was devoted to the contribution of alkoxy substituents on the relative thermodynamic stabilities of these isomeric unsaturated acetals. Comparison of the computational data with previous experimental findings shows both the enthalpies and entropies of the a b isomerization to be accurately predictable by the DFT calculations. Most importantly, the good agreement between experiment and theory proved also to be applicable to the previously observed unexpectedly large effect of 2-alkoxy substitution on the isomer equilibria.     

Relative Stabilities and Molecular Structures of the Geometrical Isomers of α,α′-Dioxasubstituted Cycloalkylidenecycloalkanes. A DFT Study

The relative stabilities and molecular structures of the geometrical isomers of seven ,-dioxa derivatives of cycloalkylidenecycloalkanes with 3to 6-membered rings have been studied by DFT calculations at the B3LYP/6-31G* level of theory. In each case, the E form was calculated to have the lower total energy. The relative energy of the Z isomer proved to increase regularly with increasing sizes of the two heterocyclic rings, ranging from 1.1 to 13.8 kJ mol^–1 on going from the 3,3to the 6,6-membered rings. Intermediate values of the relative energy were calculated for the Z forms of compounds containing two dissimilar rings. The relative energy of the Z isomer was found to be proportional to d ^–9.3, where d = the distance separating the two O atoms of the Z compound. The molecular structures, electric dipole moments, and atomic charges on the O atoms are also discussed.