DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

Flame-retardant effect of cross-linked phosphazene derivatives and pentaerythritol derivatives on polypropylene

Journal of Thermal Analysis and Calorimetry - A phosphazene-based flame retardant (PBFA) was synthesized by hexachlorocyclotriphosphazene and N-aminoethylpiperazine. To improve the flame retardancy...     

Origins of Boosted Charge Storage on Heteroatom-Doped Carbons

Although tremendous efforts have been devoted to understanding the origin of boosted charge storage on heteroatom-doped carbons, none of the present studies has shown a whole landscape. Herein, by both experimental evidence and theoretical simulation, it is demonstrated that heteroatom doping not only results in a broadened operating voltage, but also successfully promotes the specific capacitance in aqueous supercapacitors. In particular, the electrolyte cations adsorbed on heteroatom-doped carbon can effectively inhibit hydrogen evolution reaction, a key step of water decomposition during the charging process, which broadens the voltage window of aqueous electrolytes even beyond the thermodynamic limit of water (1.23 V). Furthermore, the reduced adsorption energy of heteroatom-doped carbon consequently leads to more stored cations on the heteroatom-doped carbon surface, thus yielding a boosted charge storage performance.     

Facet-dependent antibacterial activity of Au nanocrystals

Engineered nanomaterials have attracted significantly attention as one of the most promising antimicrobial agents for against multidrug resistant infections. The toxicological responses of nanomaterials are closely related to their physicochemical properties, and establishment of a structure-activity relationship for nanomaterials at the nano-bio interface is of great significance for deep understanding antibacterial toxicity mechanisms of nanomaterials and designing safer antibacterial nanomaterials. In this study, the antibacterial behaviors of well-defined crystallographic facets of a series of Au nanocrystals, including {100}-facet cubes, {110}-facet rhombic dodecahedra, {111}-facet octahedra, {221}-facet trisoctahedra and {720}-facet concave cubes, was investigated, using the model bacteria Staphylococcus aureus. We find that Au nanocrystals display substantial facet-dependent antibacterial activities. The low-index facets of cubes, octahedra, and rhombic dodecahedra show considerable antibacterial activity, whereas the high-index facets of trisoctahedra and concave cubes remained inert under biological conditions. This result is in stark contrast to the previous paradigm that the high-index facets were considered to have higher bioactivity as compared with low-index facets. The antibacterial mechanism studies have shown that the facet-dependent antibacterial behaviors of Au nanocrystals are mainly caused by differential bacterial membrane damage as well as inhibition of cellular enzymatic activity and energy metabolism. The faceted Au nanocrystals are unique in that they do not induce generation of reactive oxygen species, as validated for most antibiotics and antimicrobial nanostructures. Our findings may provide a deeper understanding of facet-dependent toxicological responses and suggest the complexities of the nanomaterial-cell interactions, shedding some light on the development of high performance Au nanomaterials-based antibacterial therapeutics.     

Effect of xylenol orange on the crystalline perfection,optical, piezoelectric and NLO behavior of unidirectionally grown imidazolium L-Tartrate single crystal

Pure and 0.1 mol% Xylenol orange (XO) doped Imidazolium L-tartrate (IMLT) nonlinear optical (NLO) single crystals were grown using Sankaranarayanan–Ramasamy (SR) method of uniaxial solution crystallization technique. The pure IMLT crystal is 100 mm in length and 15 mm in diameter. The doped IMLT crystal is 25 mm in length and 10 mm in diameter. UV–Vis-NIR spectrum shows that the pure and XO doped IMLT crystals' cut off wavelength is 235 nm. High-resolution X-ray diffraction (HRXRD) measurement and birefringence interferometry confirm that the SR method grown crystal has good crystalline perfection and optical homogeneity. The wavelength dependent refractive index and piezoelectric d₃₃ coefficient were measured. The difference refractive index (Δn) of (100) plane in parallel and perpendicular directions shows a strong dependence on wavelength. The dielectric constant, hardness and SHG conversion efficiency were also increased as a result of XO dye doping in IMLT crystal.     

Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

First principles study on the structural,electronic and phonon properties of monolayer B2Si

Using first principles density functional theory, we predict a monolayer B₂Si structure with space group Pmm2 in the present work. This structure is confirmed to be dynamically stable. Based on the plane wave pseudopotential approach, the charge density, electron localization function, density of states, energy band, phonon property and thermal conductivity of Pmm2-B₂Si are systematically studied. It is interesting that the sp² hybridization and coordination bond of Si are found in Pmm2-B₂Si, which is the most important factor for its structural stability. The density of states and energy band analysis reveals that Pmm2-B₂Si is metallic because of the partial occupied Si 3pz and B 2pz states. Moreover, the acoustic-optical coupling is important for phonon transport in Pmm2-B₂Si, and the contribution of optical modes to the lattice thermal conductivity along the [100] and [010] directions is 13% and 12%, respectively. This study gives a fundamental understanding of the structural, electronic and phonon properties in Pmm2-B₂Si.     

Planar AIEgens with Enhanced Solid-State Luminescence and ROS Generation for Multidrug-Resistant Bacteria Treatment

Planar luminogens have encountered difficulties in overcoming intrinsic aggregation-caused emission quenching by intermolecular π-π stacking interactions. Although excited-state double-bond reorganization (ESDBR) can guide us on designing planar aggregation-induced emission (AIE) luminogens (AIEgens), its mechanism has yet been elucidated. Major challenges in the field include methods to efficiently restrict ESDBR and enhance AIE performance without using bulky substituents (e.g., tetraphenylethylene and triphenylamine). In this study, we rationally developed fluoro-substituent AIEgens with stronger intermolecular H-bonding interaction for restricted molecular motions and increased crystal density, leading to decreased nonradiative decay rate by one order of magnitude. The adjusted ESDBR properties also show a corresponding response to variation in viscosity. Furthermore, their aggregation-induced reactive oxygen species (ROS) generations have been discovered. The application of such planar AIEgen in treating multidrug-resistant bacteria has been demonstrated in a mouse model. The relationship between ROS generation and distinct E/Z-configurational stacking behaviors have been further understood, providing a design principle for synthesizing planar AIEgen-based photosensitizers.     

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.