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.     

Quasi-wavelet calculations of sound scattering behind barriers

Quasi-wavelets (QWs) are a representation of turbulence consisting of self-similar, eddy-like structures with random orientations and positions in space. They are used in this paper to calculate the scattering, due to turbulent velocity fluctuations, of sound behind noise barriers as a function of the size and spatial location of the eddies. The sound scattering cross-section for QWs of an individual size class (eddy size) is derived and shown to reproduce results for the von Kármán spectrum when the scattered energies from a continuous distribution of QW sizes are combined. A Bragg resonance condition is derived for the eddy size that scatters most strongly for a given acoustic wavenumber and scattering angle. Results for scattering over barriers show that, for typical barrier conditions, most of the scattered energy originates from eddies in the size range of approximately one-half to twice the size of the eddies responsible for maximum scattering. The results also suggest that scattering over the barrier due to eddies with a line of sight to both the source and receiver is generally significant only for frequencies above several kilohertz, for sources and receivers no more than a few meters below the top of the barrier, and for very turbulent atmospheric conditions.     

Efficient and robust constitutive integrators for single-crystal plasticity modeling

Small-scale deformation phenomena such as subgrain formation, development of texture, and grain boundary sliding require simulations with a high degree of spatial resolution. When we consider finite-element simulation of metal deformation, this equates to thousands or hundreds of thousands of finite elements. Simulations of the dynamic deformations of metal samples require elastic–plastic constitutive updates of the material behavior to be performed over a small time step between updates, as dictated by the Courant condition. Further, numerical integration of physically-based equations is inherently sensitive to the step in time taken; they return different predictions as the time step is reduced, eventually approaching a stationary solution. Depending on the deformation conditions, this converged time step becomes short (10⁻⁹ s or less). If an implicit constitutive update is applied to this class of simulation, the benefit of the implicit update (i.e., the ability to evaluate over a relatively large time step) is negated, and the integration is prohibitively slow. The present work recasts an implicit update algorithm into an explicit form, for which each update step is five to six times faster, and the compute time required for a plastic update approaches that needed for a fully-elastic update. For dynamic loading conditions, the explicit model is found to perform an entire simulation up to 50 times faster than the implicit model. The performance of the explicit model is enhanced by adding a subcycling algorithm to the explicit model, by which the maximum time step between constitutive updates is increased an order of magnitude. These model improvements do not significantly change the predictions of the model from the implicit form, and provide overall computation times significantly faster than the implicit form over finite-element meshes. These modifications are also applied to polycrystals via Taylor averaging, where we also see improved model performance.     

Enzymatic polymerizations using surfactant microstructures and the preparation of polymer-ferrite composites

Applied Biochemistry and Biotechnology - Horseradish peroxidase has been used as a biocatalyst to synthesize a polymeric material from alkyl-substituted phenols. The synthesis is carried out in a...     

Synthesis of silver nanoparticles supported on silica aerogel using gamma radiolysis

Silver clusters on SiO₂ support have been synthesized using ⁶⁰Co gamma radiation. The irradiation of Ag⁺ in aqueous suspension of SiO₂ in the presence of 0.2 mol dm⁻³ isopropanol resulted in the formation of yellow suspension. The absorption spectrum showed a band at 408 nm corresponding to typical characteristic surface plasmon resonance of Ag nanoparticles. The effect of Ag⁺ concentration on the formation of Ag cluster indicated that the size of Ag clusters vary with Ag⁺ concentration, which was varied from 4×10⁻⁴ to 5×10⁻³ mol dm⁻³. The results showed that Ag clusters are stable in the pH range of 2–9 and start agglomerating in the alkaline region at pH above 9. The effect of radiation dose rate and ratio of Ag⁺/SiO₂ on the formation of Ag clusters have also been investigated. The prepared clusters have been characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), which showed the particle size of Ag clusters to be in the range of 10–20 nm.     

Viscoelastic response and interlaminar delamination resistance of epoxy/glass fiber/functionalized graphene oxide multi-scale composites

Graphene oxide (GO) was functionalized using three different diamines, namely ethylenediamine (EDA), 4,4′-diaminodiphenyl sulfone (DDS) and p-phenylenediamine (PPD) to reinforce an epoxy/glass fiber (EP/GF) composite laminate, with the aim of improving the overall composite mechanical performance. Different mechanical characterization techniques were used to determine the mechanical performance, including: tensile stress strain, double cantilever beam (DCB) mode-I fracture toughness and dynamic mechanical thermal analysis (DMTA). Scanning electron microscopy (SEM) was used to support the results and conclusions. The results demonstrated remarkable enhancements in the mechanical performance of EP/GF composite laminates by incorporation of functionalized graphene oxide (FGO) nanofiller, whilst the mechanical performance of the GO reinforced composite only improved marginally. Finally, the mechanical performance of the EP/GF/FGO multi-scale composites was found to be dependent on the type of FGO functional groups; of which EDA exhibited the highest performance. These investigations confirmed that the EDA-FGO-reinforced EP/GF composites possess excellent potential to be used as multifunctional engineering materials in industrial applications.     

Monitoring of Airborne Organic Vapors Using Ion Mobility Spectrometry

Abstract

Automated, continuous monitoring of organic vapors in air under three field designs for plume drift was demonstrated using a hand-held ion mobility spectrometer (IMS) in characterizing IMS behavior as a point sensor. In one field study, the IMS was placed 50cm from a 9m² grass plot contaminated with methylsalicylate and response to airborne vapors was recorded during a 13hr period of atmospheric turbulence to illustrate susceptibility of point sensors to wind direction. A similar study under near-quiescent atmospheric conditions was made using dimethylsulfoxide. In a third study, the plume from a point source of dipropyleneglycolmonomethylether was interrogated over a 25m × 12m grid downwind with windspeeds of 6–18km h^?. Laboratory studies were used to measure instrumental response times and influences from potentially interfering atmospheric organic pollutants.     

Three-dimensional manganese dioxide-functionalized carbon nanotube electrodes for electrochemical supercapacitors

Three-dimensional manganese dioxide (MnO₂)-functionalized multiwalled carbon nanotube (MWCNT) electrodes have been produced by a simple and scalable thermal decomposition process. The electrodes are prepared by treating planar MWCNT sheets with manganese(II) nitrate (Mn(NO₃)₂) solution and annealing at low temperature (200–300 °C) and ambient pressure. The morphology, chemical composition, and structure of the resulting matrices have been investigated with scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray diffraction. Supercapacitors assembled with three-dimensional electrodes exhibit a 14-fold increase in specific capacitance (C _sp) in comparison to those containing pristine, two-dimensional MWCNT electrodes. C _sp varies linearly with Mn(NO₃)₂ thermal decomposition temperature (from 100 to 61 F/g at 0.2 A/g), a trend that is discussed in the context of nitrate reaction chemistry and MWCNT structure. This efficient and promising approach allows for simultaneous enhancement of electrode–electrolyte contact area and incorporation of redox-based charge storage within electrochemical capacitors.     

Isoregic Thienylene‐Phenylene Polymers: The Effects of Structural Variation and Application to Photovoltaic Devices

Isoregic conjugated polymers composed of thiophene and dialkoxybenzene units were designed to harvest incident light in the mid‐visible energy range (band gap of 2.1 eV). Poly(1,4‐bis(2‐thienyl)‐2,5‐diheptoxybenzene) (PBTB(OC₇H₁₅)₂) and poly(1,4‐bis(2‐thienyl)‐2,5‐didodecyloxybenzene) (PBTB(OC₁₂H₂₅)₂) have shown significant photovoltaic performance as an electron donor when used in tandem with the electron acceptor [6, 6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) in bulk hetero‐junction photovoltaic devices. Photovoltaic devices incorporating PBTB(OC₇H₁₅)₂ and PCBM have shown AM1.5 efficiencies of ～0.6% with a short circuit current density of 2.5 mA/cm², an open circuit voltage of 0.74 V, and a fill factor of 0.32. Incident Photon‐to‐Current Efficiency (IPCE) of the device was found to be ca. 16% at 410 nm. In order to examine the relationship between the molecular structure of the polymers and their electronic energy levels, and to correlate this with photovoltaic performance, optoelectronic and electrochemical results are discussed in relation to the I‐V characteristics of the devices. Additionally, a computer‐aided simulation is used to gain further insight into the effect of polymer structure on the energetic relationships in the bulk heterojunction devices.     

Investigation of the Interaction Between N-benzyl Piperidones and Bovine Serum Albumin by Spectroscopic Approaches

Fluorescence and ultraviolet spectroscopies were applied to investigate the interaction between five N-benzyl piperidones (NBP) and bovine serum albumin (BSA) under imitated physiological conditions. The experimental results show that these NBPs have a static fluorescence quenching effect on the endogenous fluorescence of BSA at the temperatures 302 and 310?K. According to the fluorescence quenching theory, the Stern?CVolmer quenching constant (K _SV), the binding constant (K _a), and the number of binding sites (n) were obtained. Also, the effect of substituents on the binding capacity between NBP and BSA is in the order: C₆H₅?<?4-CH₃OC₆H₄?<?4-CH₃C₆H₄?<?2,4-Cl₂C₆H₃?<?4-ClC₆H₄. The corresponding thermodynamic parameters (??G, ??H, and ??S) were obtained at two different temperatures and indicate that hydrogen bonding and van der Waals forces play main roles in stabilizing the BSA?CNBP complex. The binding distance between the tryptophan residue in BSA and NBP was found to be much <7?nm based on the F?rster theory of non-radiation energy transfer. The effect of NBP on the conformation of BSA was analyzed as well by synchronous fluorescence spectroscopy.