Synthesis,structure and property of diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene]tyrosinates

Five new diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene] tyrosinates, R₂Sn[2‐O‐3‐MeOC₆H₃CH=NCH (CH₂C₆H₄OH‐4)COO] (R = Me, 1 ; Et, 2 ; Bu, 3 ; Cy, 4 ; Ph, 5 ), have been synthesized and characterized by elemental analysis, IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectra, and the X‐ray single crystal diffraction. In non‐coordinated solvent, complexes 1 – 5 have penta‐coordinated tin atom. In the solid state, 1 – 3 are centrosymmetric dimmers in which each tin atom is seven‐coordinated in a distorted pentagonal bipyramid, and 4 displays discrete molecular structure with distorted trigonal bipyramidal geometry, and the tin atom of 5 is hexa‐coordinated and possess the distorted octahedral geometry with a coordinational methanol molecule. The intermolecular O‐H???O hydrogen bonds in 1 – 4 link molecules into the different one‐dimensional supramolecular chain with R₂² (30) or R₂² (20) macrocycles, and the molecules of 5 are joined into a two‐dimensional supramolecular network containing R₄⁴ (24) and R₄⁴ (28) two macrocycles. Bioassay results against human tumour cell HeLa indicated that 3 ‐ 5 belonged to the efficient cytostatic agents and the activity decreased in the order 4 > 3 > 5 > 2 > 1. The fluorescence determinations show the complexes may be explored for potential luminescent materials.     

Synthesis,crystal structure and antifungal activity of a divalent cobalt(II) complex with uniconazole

Azole compounds have attracted commercial interest due to their high bactericidal and plant‐growth‐regulating activities. Uniconazole [or 1‐(4‐chlorophenyl)‐4,4‐dimethyl‐2‐(1H‐1,2,4‐triazol‐1‐yl)pent‐1‐en‐3‐ol] is a highly active 1,2,4‐triazole fungicide and plant‐growth regulator with low toxicity. The pharmacological and toxicological properties of many drugs are modified by the formation of their metal complexes. Therefore, there is much interest in exploiting the coordination chemistry of triazole pesticides and their potential application in agriculture. However, reports of complexes of uniconazole are rare. A new cobalt(II) complex of uniconazole, namely dichloridotetrakis[1‐(4‐chlorophenyl)‐4,4‐dimethyl‐2‐(1H‐1,2,4‐triazol‐1‐yl‐κN⁴)pent‐1‐en‐3‐ol]cobalt(II), [CoCl₂(C₁₅H₁₈ClN₃O)₄], was synthesized and structurally characterized by element analysis, IR spectrometry and X‐ray single‐crystal diffraction. The crystal structural analysis shows that the Co^II atom is located on the inversion centre and is coordinated by four uniconazole and two chloride ligands, forming a distorted octahedral geometry. The hydroxy groups of an uniconazole ligands of adjacent molecules form hydrogen bonds with the axial chloride ligands, resulting in one‐dimensional chains parallel to the a axis. The complex was analysed for its antifungal activity by the mycelial growth rate method. It was revealed that the antifungal effect of the title complex is more pronounced than the effect of fungicide uniconazole for Botryosphaeria ribis, Wheat gibberellic and Grape anthracnose.     

Relationship between liquid crystalline phase stability and ingredient composition in liquid crystal oil–water emulsion

In this study, we postulated that the optical retardation magnitude could be used to evaluate the stability of the LC phase through the Mueller matrix polarimeter method in LC emulsion. In addition, we found that the increase of cetearyl alcohol concentration induced the more periodic dense lattice structure in crystalline phase of LC lamellae and the sorbitan olivate was relatively more responsible for higher ordering in LC phase compared to C12–20 alkyl glucoside in terms of molecular parallel packing on the basis of the optical retardation magnitude. Furthermore, it was confirmed that the LC emulsion had higher skin barrier function owing to lower TEWL and higher reflectance than ordinary emulsion on human skin and maintained a uniform phase without phase separation for 8 weeks.     

Improving waterproof/breathable performance of electrospun poly(vinylidene fluoride) fibrous membranes by thermo‐pressing

Facing the ever‐increasing demand for waterproof/breathable materials, a rapid and efficient fabrication method of these functional materials with excellent performance as well as robust mechanical properties remains challenging. Herein, a simple and scalable strategy referred to as thermo‐pressing is introduced to improve the waterproof/breathable performance and mechanical properties of electrospun PVDF fibrous membranes. The synergistic effect of temperature and pressure acted on the electrospun PVDF membranes on the fiber morphology and crystal structure was investigated, which can be able to effectively enhance waterproof performance and mechanical properties, endowing the as‐prepared membranes with a modest breathability. The membranes thermo‐pressed at 150 °C with a pressure of 8.27 MPa exhibit robust tensile strength of 40.65 MPa, which is superior to those of the previous reports (below 32.8 MPa). Notably, the optimized membranes enable to show a high hydrostatic pressure of 102 kPa, good WVTR of 10.87 kg m⁻² d⁻¹ and excellent abrasion resistance, which implies that the thermo‐pressing is an efficient and facile way to steer the fiber morphology and crystal structure of electrospun membranes to improve their application performance. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 36–45     

Charge-transfer complex coupled between polymer and H-aggregate molecular crystals

Crystal needles of N,N′-bis(1-ethylpropyl)-3,4,9,10-perylenebis(dicarboximide) (EPPTC) are produced through p-stacking and are embedded in the thin film of poly(9,9-din-hexylfluorenyl-2,7-diyl) (PFO) when the blend solution of EPPTC and PFO in p-xylene is spin-coated onto a glass substrate. Charge transfer (CT) complex is resolved from the spectroscopic response of the blend film, which is generated only when the PFO molecules are excited. Thus, the PFO molecules are specified as donors and the H-aggregated EPPTC as acceptors in the formation of CT state (CTS). The emission resulting from the CTS in the red is further recognized by its much longer lifetime than both the intrinsic emission of the individual EPPTC molecules and that of their pure aggregates. Near-field analysis verifies that the CTS form on the boundary between the PFO and the crystal phases. The CT exciton forms by bounding the hole left on HOMO of the donor (PFO) and the indirectly transferred electron to the H-aggregate state of EPPTC, which transits back to the ground state by emitting a photon at about 650 nm. This introduces special physics in the heterojunctions that are coupled with the H-aggregates and mechanisms important for the design of organic photovoltaic devices. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

The Conformation of Sterically Congested Seven-Membered Rings Containing Tetracoordinate Germanium(IV): A First X-Ray Crystallographic Structure Determination

The X-ray crystallographic analysis of 6,6-dimethyl-2,4,8,10-tetra-tert-octyl-dibenzo[d,f][1,3,2]dioxagermepin, 1 is reported. In the solid-state conformation of 1, the dihedral angle about the C─C sp²-sp ² σ bond connecting the two aryl rings is 50.1°. The observed C₂ symmetry in the solid-state conformation of 1 is consistent with the previously suggested solution conformation.     

Olefin Synthesis via,the Li-Derivative of N,N,N′,N′-Tetramethyldimides of Arylmethanephosphonic Acids

Abstract

The high erythro-stereoselective reaction of Li-tetramethyldiamides of arylmethanephosphonic acids with carbonyl compounds is used for synthesis of (Z)-alkenes by thermolysis of the erythro-adducts as well as in acidic media.     

Recrystallization processes in snte thin films implanted with the nobel gas ions (Kr,Xe)

Abstract

The results of investigation of the quasi-Cherenkov (parametric) X-ray emission of 4.5 GeV electrons in diamond and quartz crystals are presented. A noticeable increase in X-ray photons yield has been observed under the influence of external factors (acoustic waves, temperature gradient).     

Self‐Assembling,Bioinspired Wax Crystalline Surfaces with Time‐Dependent Wettability

One of the most fascinating properties of materials in nature is the superhydrophobic and self‐cleaning capabilities of different plant surfaces. This is usually achieved by the hydrophobic cuticles that are made of cutin and contain wax crystals both within them and on their surfaces. Here, bioinspired n‐hexatriacontane wax films are deposited via thermal evaporation and it is shown that the surface evolves in time via self‐assembly. This leads to a dramatic change in the wetting properties with a transition from hydrophobic to superhydrophobic characteristics, which takes place within several days at room temperature. This phenomenon is investigated and strain‐induced recrystallization is proposed to be the mechanism for it. This work could become the basis for the inspiration and production of tuned, time‐dependant, temperature‐sensitive, variable‐wettability surfaces.     

Liquid-crystalline fork-like dendrons

ABSTRACT

Dendritic molecules having several rigid-rod moieties can be applied to induce liquid crystallinity for a variety of non-mesomorphic functional molecules such as metal complexes, nanoparticles, fullerenes and π-conjugated molecules when these dendritic molecules are covalently bonded to those non-mesomorphic molecules. These complex molecules are called supermolecular liquid crystals. Due to the cooperation of several mesogenic moieties, these dendritic molecules exhibit very stable liquid-crystalline (LC) phases. We have used fork-shaped LC dendrons having two or three rigid-rod moieties to induce liquid crystallinity for functional molecules such as interlocked molecules and π-conjugated molecules. In these fork-like molecules, the rigid-rod cores are attached to the 3,4,5-position of the phenyl moieties through flexible spacer, and these molecules are bonded to functional molecules through the 1-position. They basically form smectic LC phases, which induce the layered arrangement of functional moieties. Here we report on a new family of fork-like mesogens containing a hydrogen bonding moiety or an ionic group. They are designed to build supramolecular materials.