Chemical network algorithms for the risk assessment and management of chemical threats

A network of chemical threats: Current regulatory protocols are insufficient to monitor and block many short-route syntheses of chemical weapons, including those that start from household products. Network searches combined with game-theory algorithms provide an effective means of identifying and eliminating chemical threats. (Picture: an algorithm-detected pathway that yields sarin (bright red node) in three steps from unregulated substances.).     

Great expectations: can artificial molecular machines deliver on their promise?

The development and fabrication of mechanical devices powered by artificial molecular machines is one of the contemporary goals of nanoscience. Before this goal can be realized, however, we must learn how to control the coupling/uncoupling to the environment of individual switchable molecules, and also how to integrate these bistable molecules into organized, hierarchical assemblies that can perform significant work on their immediate environment at nano-, micro- and macroscopic levels. In this tutorial review, we seek to draw an all-important distinction between artificial molecular switches which are now ten a penny-or a dime a dozen-in the chemical literature and artificial molecular machines which are few and far between despite the ubiquitous presence of their naturally occurring counterparts in living systems. At the single molecule level, a prevailing perspective as to how machine-like characteristics may be achieved focuses on harnessing, rather than competing with, the ineluctable effects of thermal noise. At the macroscopic level, one of the major challenges inherent to the construction of machine-like assemblies lies in our ability to control the spatial ordering of switchable molecules-e.g., into linear chains and then into muscle-like bundles-and to influence the cross-talk between their switching kinetics. In this regard, situations where all the bistable molecules switch synchronously appear desirable for maximizing mechanical power generated. On the other hand, when the bistable molecules switch "out of phase," the assemblies could develop intricate spatial or spatiotemporal patterns. Assembling and controlling synergistically artificial molecular machines housed in highly interactive and robust architectural domains heralds a game-changer for chemical synthesis and a defining moment for nanofabrication.     

Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S‐Shaped Aza[5]helicene Motifs

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S‐shaped aza[5]helicene.     

From holes to sponge at irradiated Ge surfaces with increasing ion energy—an effect of defect kinetics?

We show that hole patterns and sponge-like layers at irradiated Ge surfaces originate from the same driving force, namely the kinetics of ion beam induced defects in the amorphous Ge surface layer. Ge hole patterns reported earlier for irradiation with low energy (5 keV) Ga⁺ ions were reproduced for low energy Bi⁺ but also for Ge⁺ self-irradiation, which proves that the dominating driving force for morphology evolution cannot originate from the implanted impurities. At higher ion energies the well-known formation of sponge-like Ge surface layers after heavy ion irradiation was found for Bi⁺ irradiation and Ge⁺ self-irradiation, also. The transition from smooth surfaces via hole patterns to sponge-like morphologies with increasing ion energies was studied in detail. A model based on the kinetics of ion beam induced defects was developed and implemented in 3D kinetic Monte Carlo simulations, which reproduce the transition from hole patterns to sponge-like layers with increasing ion energy.     

Limit theorems for random walks

We consider a random walk $S_{\tau }$ which is obtained from the simple random walk $S$ by a discrete time version of Bochner’s subordination. We prove that under certain conditions on the subordinator $\tau$ appropriately scaled random walk $S_{\tau }$ converges in the Skorohod space to the symmetric $\alpha$-stable process $B^{\alpha }$. We also prove asymptotic formula for the transition function of $S_{\tau }$ similar to the Pólya’s asymptotic formula for $B^{\alpha }$.     

Experimental verification of heat transfer coefficient for nucleate boiling at sub-atmospheric pressure and small heat fluxes

In this paper we study the influence of sub-atmospheric pressure on nucleate boiling. Sixteen correlations for pool boiling available in literature are gathered and evaluated. Analysis is performed in the pressure range 1–10 kPa and for heat flux densities 10–45 kW/m². Superheats are set between 6.2 and 28.7 K. The results of calculations were compared with experimental values for the same parameters. The experiments were conducted using isolated glass cylinder and water boiling above the copper plate. Results show that low pressure adjust the character of boiling curve—the curve flattened and the natural convection region of boiling is shifted towards higher wall temperature superheats due to the influence of low pressure on the bubble creation and process of its departure. In result, 8 of 16 analyzed correlations were determined as completely invalid in subatmospheric conditions and the remaining set of equations was compared to experimental results. Experimentally obtained values of heat transfer coefficients are between 1 and 2 kW/m²K. With mean absolute deviation (MAD) we have found that the most accurate approximation of heat transfer coefficient is obtained using Mostinski reduced pressure correlation (0.13–0.35 MAD) and Labuntsov correlation (0.12–0.89 MAD).     

Tetra­kis(1‐eth­yl‐1H‐1,2,4‐triazole‐κN4)bis­(nitrato‐κO)copper(II) and bis­(nitrato‐κO)tetra­kis­(1‐prop­yl‐1H‐1,2,4‐triazole‐κN4)copper(II)

The copper(II) environments for tetra­kis­(1‐eth­yl‐1,2,4‐triaz­ole)­dinitratocopper(II), [Cu(NO₃)₂(C₄H₇N₃)₄], and tetrakis­(1‐prop­yl‐1,2,4‐triazole)dinitratocopper(II), [Cu(NO₃)₂(C₅H₉N₃)₄], are distorted square bipyramidal. Both structures are centrosymmetric, with the copper(II) ions located at inversion centers coordinated by four N atoms of four triazole mol­ecules and by two O atoms of two nitrate ions in an elongated octa­hedral geometry. This elongation is a result of the Jahn–Teller effect. The largest distortion is that of the N—Cu—O angles, which differ from 90° by 5.68 (10)° in the eth­yl and 5.59 (8)° in the prop­yl derivative.     

Self-assembly of gears at a fluid/air interface

This paper describes a dynamic system-a system that develops order only when dissipating energy-comprising millimeter to centimeter scale gears that self-assemble into a simple machine at a fluid/air interface. The gears are driven externally and indirectly by magnetic interactions; they are made of poly(dimethylsiloxane) (PDMS) or magnetically doped PDMS, and fabricated by soft lithography. Transfer of torque between gears can take place through three different mechanisms: mechanical interaction, hydrodynamic shear, and capillarity/overlap of menisci. Interplay between these forces allows interactions and motions that are not possible with conventional systems of gears.