Defining graphenic crystallites in disordered carbon: moving beyond the platelet model

We develop a picture of graphenic crystallites within disordered carbons that goes beyond the traditional model of graphitic platelets at random orientation. Using large atomistic models containing one million atoms, we redefine the meaning of the quantity La extracted from X-ray diffraction (XRD) patterns. Two complementary approaches are used to measure the size of graphenic crystallites, which are defined as regions of regularly arranged hexagons. Firstly, we calculate the X-ray diffraction pattern directly from the atomistic coordinates of the structure and analyse them following a typical experimental process. Second, the graphenic crystallites are identified from a direct geometrical approach. By mapping the structure directly, we replace the idealised picture of the crystallite with a more realistic representation of the material and provide a well-defined interpretation for $L_a$ measurements of disordered carbon. A key insight is that the size distribution is skewed heavily towards small fragments, with more than 75% of crystallites smaller than half of $L_a$

Using Plasma Etching to Access the Polymer Density Distribution and Diffusivity of Gel Particles

In this paper we examine the polymer density distribution of gel particles and its effect on solvent diffusivity through the polymer network. In order to access the inner particle regions, external polymer layers were removed by plasma etching, thus reducing them from the outside. Higher polymer densities after erosion showed internal heterogeneity, with the density increasing towards the center of the particles. An exponential decay polymer density model is proposed, and the spatial relaxation length measured. The diffusion of solvent through the particles, before and after the plasma oxidation, revealed a correlation between the diffusion coefficient and the internal density

Deciphering the Chemical Basis of Nestmate Recognition

Social insects maintain colony cohesion by recognizing and, if necessary, discriminating against conspecifics that are not part of the colony. This recognition ability is encoded by a complex mixture of cuticular hydrocarbons (CHCs), although it is largely unclear how social insects interpret such a multifaceted signal. CHC profiles often contain several series of homologous hydrocarbons, possessing the same methyl branch position but differing in chain length (e.g., 15-methyl-pentatriacontane, 15-methyl-heptatriacontane, 15-methyl-nonatriacontane). Recent studies have revealed that within species these homologs can occur in correlated concentrations. In such cases, single compounds may convey the same information as the homologs. In this study, we used behavioral bioassays to explore how social insects perceive and interpret different hydrocarbons. We tested the aggressive response of Argentine ants, Linepithema humile, toward nest-mate CHC profiles that were augmented with one of eight synthetic hydrocarbons that differed in branch position, chain length, or both. We found that Argentine ants showed similar levels of aggression toward nest-mate CHC profiles augmented with compounds that had the same branch position but differed in chain length. Conversely, Argentine ants displayed different levels of aggression toward nest-mate CHC profiles augmented with compounds that had different branch positions but the same chain length. While this was true in almost all cases, one CHC we tested elicited a greater aggressive response than its homologs. Interestingly, this was the only compound that did not occur naturally in correlated concentrations with its homologs in CHC profiles. Combined, these data suggest that CHCs of a homologous series elicit the same aggressive response because they convey the same information, rather than Argentine ants being unable to discriminate between different homologs. This study contributes to our understanding of the chemical basis of nestmate recognition by showing that, similar to spoken language, the chemical language of social insects contains “synonyms,” chemicals that differ in structure, but not meaning

Plasmonic communications : light on a wire

The emerging field of plasmonics promises the generation, processing, transmission, sensing and detection of signals at optical frequencies along metallic surfaces much smaller than the wavelengths they carry. Plasmonic technology has applications in a wide range of fields, including biophotonics, sensing, chemistry and medicine. But perhaps the area where it will have the most profound impact is in optical communications, since plasmonic waves oscillate at optical frequencies and thus can carry information at optical bandwidths

On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes

Herein we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes, using both experimental and computational methods. The dissociation of [{Au(NHC)}2(µ-OH)][BF4] is essential to enter the catalytic cycle; this step is favored in the presence of bulky, non-coordinating counterions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but as a co-catalyst, lowering the energy barriers for several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an ‘off-cycle’ rather than an ‘in-cycle’ intermediate

Ultrasensititve system for the real time detection of H2O2 based on strong coupling in a bio-plasmonic system

We theoretically investigate the dependence of the different parameters of an optical biosensor for the detection of Hydrogen peroxide (H2O2) based on absorption enhancement of Cytochrome c molecules near gold nanoparticles. H2O2 is a major reactive oxygen species which is involved in signaling pathways and oxidative stress in cells. We use the Green's function approach as well as confirm the corresponding simulation results using the surface integral formulation. Further we show that this technique can be applied for detection of other small molecules, like oxygen and carbon monoxide