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.     

Divergent Synthesis of Oxa-Cyclic Nitrones through Gold(I)-Catalyzed 1,3-Azaprotio Transfer of Propargylic α-Ketocarboxylate Oximes: Experimental and DFT Studies

1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. The incorporation of an oxygen atom to the chain of alkynyl oximes led to the formation of two different oxa-cyclic nitrones. It was found that internal alkynyl oximes with an E-configuration deliver five-membered nitrones, whereas terminal alkynyl oximes with an E-configuration afford six-membered nitrones. DFT calculations on four possible pathways supported a stepwise formation of C−N and C−H bonds, in which a 1,3-acyloxy-migration competes with the 1,3-azaprotio-transfer, especially in the case of internal alkynyl oximes. The relative nucleophilic properties of oxygen in the carbonyl group and the nitrogen in the oxime, the electronic effects of alkynes, and the influence of the ring system have been investigated computationally.     

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.     

Norbornene derivatives from a metal‐free,strain‐promoted cycloaddition reaction: New building blocks for ring‐opening metathesis polymerization reactions

The preparation of new ring opening metathesis polymerization (ROMP) monomers using a 1,3‐dipolar cycloaddition between aryl azides and norbornadiene is described. Various norbornenetriazolines, obtained through a solvent‐and catalyst‐free reaction, can subsequently be incorporated into polymer backbones through ROMP reactions. Furthermore, thermal decomposition of the triazoline moiety can allow for further polymer functionalization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2357–2362     

Prasad L. Polavarapu (Ed.): Chiral analysis: advances in spectroscopy,chromatography, and emerging methods, 2nd ed.

Analytical and Bioanalytical Chemistry -     

Dynamic Variation of Excitonic Coupling in Excited Bilayer Graphene Quantum Dots?

The intermolecular interaction determines the photophysical properties of the organic aggregates, which are critical to the performance of organic photovoltaics. Here, excitonic coupling, an important intermolecular interaction in organic aggregates, between the π-stacking graphene quantum dots is studied by using transient absorption spectroscopy. We find that the spectral evolution of the ground state bleach arises from the dynamic variation of the excitonic coupling in the excited π-stacks. According to the spectral simulations, we demonstrate that the kinetics of the vibronic peak can be exploited as a probe to measure the dynamics of excitonic coupling in the excited π-stacks.     

Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.