EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposedPublisher PDFPeer reviewe

Frustration of crystallisation by a liquid–crystal phase

Frustration of crystallisation by locally favoured structures is critically important in linking the phenomena of supercooling, glass formation, and liquid-liquid transitions. Here we show that the putative liquid-liquid transition in n-butanol is in fact caused by geometric frustration associated with an isotropic to rippled lamellar liquid-crystal transition. Liquid-crystal phases are generally regarded as being “in between” the liquid and the crystalline state. In contrast, the liquid-crystal phase in supercooled n-butanol is found to inhibit transformation to the crystal. The observed frustrated phase is a template for similar ordering in other liquids and likely to play an important role in supercooling and liquid-liquid transitions in many other molecular liquids

Abstract Machines for Dynamic Computation

Laboratory for Foundations of Computer ScienceIn this thesis we address the challenges associated with the provision of dynamic software architectures. These are systems in which programs are constructed from separately compiled units with a facility for the replacement of these units at runtime. Typical examples of applications which will benefit from this dynamic approach are long-lived systems in which downtime is highly undesirable, for example, web-servers, database engines, and equipment controllers. In addition, dynamic software architectures are also gaining popularity with the recent advent of wide-area Internet applications, where it is often impractical to compile a program in its entirety or begin execution in a single step. Our approach to dynamic software architectures differs from earlier attempts in that we guarantee the safety of the replacement operation. This is done by founding our techniques on the rigour of strong typing. In the first half of the thesis we take an existing static software architecture with strong typing facilities and modular program construction, namely the Standard ML platform, and equip it with facilities for separate-compilation and code-replacement of modules. The resulting dynamic software architecture, which we call Dynamic ML, ensures the safety of replacement through an effective use of state-of-the-art advances in the fields of types in compilation and abstract machines. In the latter half of the thesis we extend Dynamic ML with a facility for distributed execution and adapt our code-replacement model accordingly. This will permit the construction of larger dynamic architectures, for example, across a distributed network of workstations. We also perform a mechanical verification of the distributed algorithm by model checking, to gain further confidence in the correctness of our approach. At the end of the thesis we outline an implementation of our techniques for the Java language, demonstrating the portability of our approach

Etching with Electron Beam Generated Plasmas

A modulated electron beam generated plasma has been used to dry etch standard photoresist materials and silicon. Oxygen–argon mixtures were used to etch organic resist material and sulfur hexafluoride mixed with argon or oxygen was used for the silicon etching. Etch rates and anisotropy were determined with respect to gas compositions, incident ion energy (from an applied rf bias) and plasma duty factor. For 1818 negative resist and i-line resists the removal rate increased nearly linearly with ion energy (up to 220 nm/min at 100 eV), with reasonable anisotropic pattern transfer above 50 eV. Little change in etch rate was seen as gas composition went from pure oxygen to 70% argon, implying the resist removal mechanism in this system required the additional energy supplied by the ions. With silicon substrates at room temperature, mixtures of argon and sulfur hexafluoride etched approximately seven times faster (1375 nm/min) than mixtures of oxygen and sulfur hexafluoride (,200 nm/min) with 200 eV ions, the difference is attributed to the passivation of the silicon by involatile silicon oxyfluoride sSiOxFyd compounds. At low incident ion energies, the Ar–SF6 mixtures showed a strong chemical (lateral) etch component before an ion-assisted regime, which started at ,75 eV. Etch rates were independent of the 0.5%–50% duty factors studied in this work

Etching with Electron Beam Generated Plasmas

A modulated electron beam generated plasma has been used to dry etch standard photoresist materials and silicon. Oxygen–argon mixtures were used to etch organic resist material and sulfur hexafluoride mixed with argon or oxygen was used for the silicon etching. Etch rates and anisotropy were determined with respect to gas compositions, incident ion energy (from an applied rf bias) and plasma duty factor. For 1818 negative resist and i-line resists the removal rate increased nearly linearly with ion energy (up to 220 nm/min at 100 eV), with reasonable anisotropic pattern transfer above 50 eV. Little change in etch rate was seen as gas composition went from pure oxygen to 70% argon, implying the resist removal mechanism in this system required the additional energy supplied by the ions. With silicon substrates at room temperature, mixtures of argon and sulfur hexafluoride etched approximately seven times faster (1375 nm/min) than mixtures of oxygen and sulfur hexafluoride (,200 nm/min) with 200 eV ions, the difference is attributed to the passivation of the silicon by involatile silicon oxyfluoride sSiOxFyd compounds. At low incident ion energies, the Ar–SF6 mixtures showed a strong chemical (lateral) etch component before an ion-assisted regime, which started at ,75 eV. Etch rates were independent of the 0.5%–50% duty factors studied in this work

Effect of Plasma Flux Composition on the Nitriding Rate of Stainless Steel

The total ion flux and nitriding rate for stainless steel specimens exposed to a modulated electron beam generated argon-nitrogen plasma were measured as a function of distance from the electron beam axis. The total ion flux decreased linearly with distance, but the nitriding rate increased under certain conditions, contrary to other ion flux/nitriding rate comparisons published in the literature. Variation in ion flux composition with distance was explored with a mass spectrometer and energy analyzer as a possible explanation for the anomalous nitriding rate response to ion flux magnitude. A transition in ion flux composition from mostly N2 1 to predominantly N1 ions with increasing distance was observed. Significant differences in molecular and atomic nitrogen ion energy distributions at a negatively biased electrode were also measured. An explanation for nitriding rate dependence based on flux composition and magnitude is proposed

Photothermal colloid antibodies for shape-selective recognition and killing of microorganisms

We have developed a class of selective antimicrobial agents based on the recognition of the shape and size of the bacterial cells. These agents are anisotropic colloid particles fabricated as negative replicas of the target cells which involve templating of the cells with shells of inert material followed by their fragmentation. The cell shape recognition by such shell fragments is due to the increased area of surface contact between the cells and their matching shell fragments which resembles antibody-antigen interaction. We produced such "colloid antibodies" with photothermal mechanism for shape-selective killing of matching cells. This was achieved by the subsequent deposition of (i) gold nanoparticles (AuNPs) and (ii) silica shell over yeast cells, which were chosen as model pathogens. We demonstrated that fragments of these composite AuNP/silica shells act as "colloid antibodies" and can bind to yeast cells of the same shape and size and deliver AuNPs directly onto their surface. We showed that after laser irradiation, the localized heating around the AuNPs kills the microbial cells of matching shape. We confirmed the cell shape-specific killing by photothermal colloid antibodies in a mixture of two bacterial cultures of different cell shape and size. This approach opens a number of avenues for building powerful selective biocides based on combinations of colloid antibodies and cell-killing strategies which can be applied in new antibacterial therapies

ElAM: A computer program for the analysis and representation of anisotropic elastic properties

Copyright © 2010 Elsevier. NOTICE: this is the author’s version of a work that was accepted for publication in Computer Physics Communications. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Computer Physics Communications, Volume 181, Issue 12 (2010), DOI: 10.1016/j.cpc.2010.08.033The continuum theory of elasticity has been used for more than a century and has applications in many fields of science and engineering. It is very robust, well understood and mathematically elegant. In the isotropic case elastic properties are easily represented, but for non-isotropic materials, even in the simple cubic symmetry, it can be difficult to visualise how properties such as Young's modulus or Poisson's ratio vary with stress/strain orientation. The ElAM (Elastic Anisotropy Measures) code carries out the required tensorial operations (inversion, rotation, diagonalisation) and creates 3D models of an elastic property's anisotropy. It can also produce 2D cuts in any given plane, compute averages following diverse schemes and query a database of elastic constants to support meta-analyses. Program summary Program title: ElAM1.0 Catalogue identifier: AEHB_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEHB_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 43 848 No. of bytes in distributed program, including test data, etc.: 2 498 882 Distribution format: tar.gz Programming language: Fortran90 Computer: Any Operating system: Linux, Windows (XP, Vista) RAM: Depends chiefly on the size of the arrays representing elastic properties in 3D Classification: 7.7 Nature of problem: Representation of elastic moduli and ratios, and of wave velocities, in 3D; automatic discovery of unusual elastic properties. Solution method: Stiffness matrix (6×6)(6×6) inversion and conversion to compliance tensor (3×3×3×3)(3×3×3×3), tensor rotation, dynamic matrix diagonalisation, simple optimisation, postscript and VRML output preparation. Running time: Dependent on angular accuracy and size of elastic constant database (from a few seconds to a few hours). The tests provided take from a few seconds for test0 to approximately 1 hour for test4

Brillouin scattering study on the single-crystal elastic properties of natrolite and analcime zeolites

Copyright © 2005 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Journal of Applied Physics 98 (2005) and may be found at http://link.aip.org/link/?jap/98/053508The Brillouin light-scattering technique was used to investigate the single-crystal elastic properties of two aluminosilicate zeolites, natrolite (NAT) and analcime (ANA), at ambient conditions. An inversion of the acoustic velocity data results in the full set of elastic stiffness moduli (Cij's) for both materials. From the single-crystal moduli the aggregate adiabatic bulk moduli (Ks), shear moduli (G), and Poisson's ratios (v) were found to be Ks=48.5(1.0) GPa, G=31.6(1.0) GPa, and v =0.232(5) for NAT, and Ks=59.8(1.2) GPa, G=32.1(1.0) GPa, and v=0.272(5) for ANA (Voigt-Reuss-Hill averages). The bulk and shear moduli of both zeolites are relatively low compared with those of densely packed aluminosilicates, reflecting an open framework structure of (Al,SiO4) tetrahedra which is easily deformed by bending the Si–O–Al angles. As expected for a less dense crystal, NAT is softer and more compressible than ANA. An evaluation of the directional Young's moduli shows that the compressibility of NAT is nearly uniform along the [100] and [010] axes, while [001] is stiffer, in agreement with previous compression studies. We do not find experimental evidence of negative Poisson's ratios for NAT zeolites as predicted by recent theoretical calculations

Applying Recent Argumentation Methods to Some Ancient Examples of Plausible Reasoning

Plausible (eikotic) reasoning known from ancient Greek (late Academic) skeptical philosophy is shown to be a clear notion that can be analyzed by argu- mentation methods, and that is important for argumentation studies. It is shown how there is a continuous thread running from the Sophists to the skeptical philosopher Carneades, through remarks of Locke and Bentham on the subject, to recent research in artificial intelligence. Eleven characteristics of plausible reasoning are specified by analyzing key examples of it recognized as important in ancient Greek skeptical philosophy using an artificial intelligence model called the Carneades Argumentation System (CAS). By applying CAS to ancient examples it is shown how plausible reasoning is especially useful for gaining a better understanding of evidential reasoning in law, and argued that it can also be applied to everyday argumentation. Our analysis of the snake and rope example of Carneades is also used to point out some ways CAS needs to be extended if it is to more fully model the views of this ancient philosopher on argumentation