Enhancement of the Curie temperature by isomerization of diarylethene (DAE) for an organic-inorganic hybrid system: Co4(OH)7(DAE)0.5.3H2O

Intercalation of an organic photochromic molecule into layered magnetic systems may provide multifunctional properties such as photomagnetism. To build up a photosensitive multifunctional magnet, an organic-inorganic hybrid system coupled with a photochromic diarylethene anion, 2,2'-dimethyl-3,3'-(perfluorocyclopentene-1,2-diyl)bis(benzo[b]thiophene-6-sulfonate) (DAE), and cobalt LDHs (layered double hydroxides), Co4(OH)7(DAE)0.5.3H2O, was synthesized by the anion exchange reaction between Co2(OH)3(CH3COO).H2O and DAE. In the dark and under UV-irradiated (313 nm) conditions, Co4(OH)7(DAE)0.5.3H2O with open and closed forms of DAE were obtained, respectively. The magnetic susceptibility measurements elucidated ferromagnetic intra- and interlayer interactions and Curie temperatures of TC = 9 and 20 K for cobalt LDHs with the open and closed forms of DAE, respectively. The enhancement of the Curie temperature from 9 to 20 K by substitution of the open form of DAE with the closed form of DAE as an intercalated molecule is attributed to the delocalization of the pi-electrons in the closed form of DAE, which enhances the interlayer magnetic interaction. The enhancement of the interlayer magnetic interaction induced by the delocalization of pi-electrons in intercalated molecules is strongly supported by the fact that the Curie temperature (26.0 K) of cobalt LDHs with (E,E)-2,4-hexadienedioate having a conjugated pi-electron system is enormously higher than that (7.0 K) of the cobalt LDHs with hexanedioate. By UV irradiation at 313 nm, Co4(OH)7(DAE)0.5.3H2O shows the photoisomerization of DAE from the open form to the closed one in the solid state, which leads to the enhancement of Curie temperature.     

Phosphorothioate Modification of mRNA Accelerates the Rate of Translation Initiation to Provide More Efficient Protein Synthesis

Messenger RNAs (mRNAs) with phosphorothioate modification (PS‐mRNA) to the phosphate site of A, G, C, and U with all 16 possible combinations were prepared, and the translation reaction was evaluated using an E. coli cell‐free translation system. Protein synthesis from PS‐mRNA increased in 12 of 15 patterns when compared with that of unmodified mRNA. The protein yield increased 22‐fold when the phosphorothioate modification at A/C sites was introduced into the region from the 5′‐end to the initiation codon. Single‐turnover analysis of PS‐mRNA translation showed that phosphorothioate modification increases the number of translating ribosomes, thus suggesting that the rate of translation initiation (rate of ribosome complex formation) is positively affected by the modification. The method provides a new strategy for improving translation by using non‐natural mRNA.     

57Fe-Mössbauer spectroscopic studies on the mixed-valence states of oxo-centered trinuclear iron(II,III, III) complexes with fatty acid anions

Oxo-Centered mixed-valence trinuclear Iron butyrates, [Fe₃O(C₃H₇CO₂)₆(py)₃]·x(py); x=0, 1, were newly synthesized and their Mössbauer spectra were determined. The temperature dependent mixed-valence state was observed in both the pyridine-solvated and the non-solvated complexes.     

Sulfur-substituted tetrahedranes

The stable sulfur-substituted tetrahedrane derivatives 2-4 were synthesized by the reaction of tris(trimethylsilyl)tetrahedranyllithium 1 with diphenyl disulfide, bis(4-nitrophenyl) disulfide, and bis(2,4-dinitrophenyl) disulfide, respectively, and characterized by both NMR spectroscopy and X-ray crystallography. Phenylsulfonyltetrahedrane 5 was prepared by the reaction of 2 and m-chloroperbenzoic acid. The UV-vis absorption spectra of 2-4 suggested an interaction of the σ orbital of the tetrahedrane core and the lone-pair electrons on the sulfur atom, whereas no interaction for 5 was found. Thermal reactions of 2 and 5 are also reported; 2 underwent fragmentation into two acetylene molecules, whereas 5 gave the corresponding cyclobutadiene.     

3-dynamic coloring of planar triangulations

An $r$-dynamic $k$-coloring of a graph $G$ is a proper $k$-coloring such that any vertex $v$ has at least $min\{r,{deg}_G\left(v\right)\}$ distinct colors in $N_G\left(v\right)$. The $r$-dynamic chromatic number${\chi }_r^d\left(G\right)$ of a graph $G$ is the least $k$ such that there exists an $r$-dynamic $k$-coloring of $G$.Loeb et al. (2018) showed that if $G$ is a planar graph, then ${\chi }_3^d\left(G\right)\le 10$, and there is a planar graph $G$ with ${\chi }_3^d\left(G\right)=7$. Thus, finding an optimal upper bound on ${\chi }_3^d\left(G\right)$ for a planar graph $G$ is a natural interesting problem. In this paper, we show that ${\chi }_3^d\left(G\right)\le 5$ if $G$ is a planar triangulation. The upper bound is sharp.     

On separable self-complementary graphs

In this paper, we describe the structure of separable self-complementary graphs.     

Diagonal Flips in Hamiltonian Triangulations on the Sphere

In this paper, we shall prove that any two Hamiltonian triangulations on the sphere with n5 vertices can be transformed into each other by at most 4n–20 diagonal flips, preserving the existence of Hamilton cycles. Moreover, using this result, we shall prove that at most 6n–30 diagonal flips are needed for any two triangulations on the sphere with n vertices to transform into each other.     

Tin-centered radical and cation: stable and free

The first stable stannyl radical (tBu2MeSi)3Sn* (1) has been synthesized by the reaction of tBu2MeSiNa with SnCl2-dioxane in diethyl ether. The X-ray crystal structure and electron paramagnetic resonance (EPR) data of this radical show that 1 has a planar geometry, being a pi-radical in both the solid and the liquid states. One-electron oxidation of 1 with Ph3C+.B(C6F5)4- in benzene quantitatively produced the corresponding cation (tBu2MeSi)3Sn+.B(C6F5)4- (2), representing the stable free stannylium ion that has been fully characterized by X-ray analysis and NMR data. Being free, 2 features a record downfield shifted resonance for stannylium ions: +2653 ppm.