Particle behavior in aesthetic field theory

We discuss the structure of a particle system obtained in “aesthetic” field theory and study the evolution of this system in time. We find the particle system to have more structure than particles found by other authors investigating particlelike behavior in nonlinear field theories. Our particle system has a maximum center in proximity to a minimum center. Thus, we can interpret our system as being constructed of two bodies. We find that the maximum center and the minimum center move in straight lines, to computer accuracy. Thus, we have not found any nontrivial force laws. This suggests that the situation with respect to basic principles be kept fluid. So far as we know, we are the first investigators to study the trajectories of a two-body system which arises as a consequence of nonlinear field equations.     

Halogen Bonding: An Interim Discussion

Halogen bonding is a noncovalent interaction that is receiving rapidly increasing attention because of its significance in biological systems and its importance in the design of new materials in a variety of areas, for example, electronics, nonlinear optical activity, and pharmaceuticals. The interactions can be understood in terms of electrostatics/polarization and dispersion; they involve a region of positive electrostatic potential on a covalently bonded halogen and a negative site, such as the lone pair of a Lewis base. The positive potential, labeled a σ hole, is on the extension of the covalent bond to the halogen, which accounts for the characteristic near‐linearity of halogen bonding. In many instances, the lateral sides of the halogen have negative electrostatic potentials, allowing it to also interact favorably with positive sites. In this discussion, after looking at some of the experimental observations of halogen bonding, we address the origins of σ holes, the factors that govern the magnitudes of their electrostatic potentials, and the properties of the resulting complexes with negative sites. The relationship of halogen and hydrogen bonding is examined. We also point out that σ‐hole interactions are not limited to halogens, but can also involve covalently bonded atoms of Groups IV–VI. Examples of applications in biological/medicinal chemistry and in crystal engineering are mentioned, taking note that halogen bonding can be “tuned” to fit various requirements, that is, strength of interaction, steric factors, and so forth.     

Computational analysis of relative stabilities of polyazine N-oxides

There is considerable interest in polyazine N-oxides as potential frameworks for energetic compounds with relatively high enthalpies of formation and crystal densities. The N⁺→O^? linkages, if appropriately located, may diminish the destabilization associated with nitrogen catenation. We have computationally characterized 40 N-oxides of the isomeric diazines, triazines, and tetrazines in terms of their geometries, relative energies, and (for a representative selection) electrostatic potentials. The presence of N⁺→O^? linkages does partially counteract the destabilizing effects of nitrogen catenation, although the isomers with complete catenation remain the least stable. The stabilizing influence of N⁺→O^? groups, and the accompanying changes in bond lengths, can be understood in terms of resonance charge delocalization to the polyazine rings. The N(O)–N(O) bonds between nitrogens that both bear oxygens tend to be relatively weak. The electrostatic potentials above the polyazine rings become increasingly positive as there are more nitrogens and oxygens; eventually they are positive above all of the carbons and nitrogens and possibly even the oxygens, with negative regions only on the peripheries of the molecules. However, the nitrogens that bear oxygens always have more positive potentials than those that do not.     

Particle Production in Reflection and Transmission Mode Laser Ablation: Implications for Laserspray Ionization

Particles were ablated from laser desorption and inlet ionization matrix thin films with a UV laser in reflection and transmission geometries. Particle size distributions were measured with a combined scanning mobility particle sizer (SMPS) and aerodynamic particle sizer (APS) system that measured particles in the size range from 10 nm to 20 μm. The matrixes investigated were 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), sinapic acid (SA), 2,5-dihydroxy-acetophenone (DHAP), and 2-nitrophloroglucinol (NPG). Nanoparticles with average diameters between 20 and 120 nm were observed in both transmission and reflection geometry. The particle mass distribution was significantly different in reflection and transmission geometry. In reflection geometry, approximately equal mass was distributed between particles in the 20 to 450 nm range of diameters and particles in the 450 nm to 1.5 μm diameter range. In transmission mode, the particle mass distribution was dominated by large particles in the 2 to 20 μm diameter range. Ablation of inlet ionization matrices DHAP and NPG produced particles that were 3 to 4 times smaller compared with the other matrices. The results are consistent with ion formation by nanoparticle melting and breakup or melting and breakup of the large particles through contact with heated inlet surfaces.

Origin and impact of particle-to-particle variations in composition measurements with the nano-aerosol mass spectrometer

In the nano-aerosol mass spectrometer, individual particles in the 10–30 nm size range are trapped and irradiated with a high pulse energy laser beam. The laser pulse generates a plasma that disintegrates the particle into atomic ions, from which the elemental composition is determined. Particle-to-particle variations among the mass spectra are shown to arise from plasma energetics: Low ionization energy species are enhanced in some spectra while high ionization energy species are enhanced in others. These variations also limit the accuracy and precision of elemental analysis, with higher deviations generally observed when low ionization energy species are dominant in the mass spectrum. For standard datasets generated from nominally identical particles, it is shown that that the error associated with composition measurement is random and that averaging the spectra from a few tens of particles is sufficient for measuring the mole fractions of common elements to within about 10 % of the expected value. Averaging a greater number of particles offers limited improvement of the measurement precision but has the deleterious effect of degrading the measurement time-resolution, which is given by the time needed to obtain the required number of particle spectra for averaging. An internally mixed ambient particle dataset was found to give a similar result to the standard datasets, that is, the measured elemental composition converged to the average value after a few tens of particles were averaged.     

Reaction of 3-Diazocamphor with Silver Ion - Formation of Tricyclanone

The usual method of formation of tricyclanone (1) involves thermolysis of an intimate mixture of 3-diazocamphor (3) and copper powder and is thought to involve ketocarbene (5).¹ Recently this method has been supplemented² by one which involves reaction of 3,3-dibromocamphor with diethylzinc in benzene where α-elimination to give ketocarbene (5) is mediated by 3-bromocamphor carbanion whose role is indicated by trapping as 3-bromocamphor; this material accounts for ca. 10% of product even after prolonged reaction times.     

Deep‐ultraviolet laser ablation electrospray ionization mass spectrometry

A 193‐nm wavelength deep ultraviolet laser was used for ambient laser ablation electrospray ionization mass spectrometry of biological samples. A pulsed ArF excimer laser was used to ablate solid samples, and the resulting plume of the desorbed material merged with charged electrospray droplets to form ions that were detected with a quadrupole time‐of‐flight mass spectrometer. Solutions containing peptide and protein standards up to 66‐kDa molecular weight were deposited on a metal target, dried, and analyzed. No fragmentation was observed from peptides and proteins as well as from the more easily fragmented vitamin B₁₂ molecule. The mass spectra contained peaks from multiply charged ions that were identical to conventional electrospray. Deep UV laser ablation of tissue allowed detection of lipids from untreated tissue. The mechanism of ionization is postulated to involve absorption of laser energy by a fraction of the analyte molecules that act as a sacrificial matrix or by residual water in the sample.     

Analysis of digital recordings of noise levels using a programmable calculator

The system used at the Building Research Station for analysing digital recordings of noise levels is described. A suite of programs has been developed which analyses the noise recordings and gives values of selected noise units. Time histories of the noise may be plotted using some of the programs.     

Comparisons of predicted steady-state levels in rooms with extended- and local-reaction bounding surfaces

A combined beam-tracing and transfer-matrix model for predicting steady-state sound-pressure levels in rooms with multilayer bounding surfaces was used to compare the effect of extended- and local-reaction surfaces, and the accuracy of the local-reaction approximation. Three rooms—an office, a corridor and a workshop—with one or more multilayer test surfaces were considered. The test surfaces were a single-glass panel, a double-drywall panel, a carpeted floor, a suspended-acoustical ceiling, a double-steel panel, and glass fibre on a hard backing. Each test surface was modeled as of extended or of local reaction. Sound-pressure levels were predicted and compared to determine the significance of the surface-reaction assumption. The main conclusions were that the difference between modeling a room surface as of extended or of local reaction is not significant when the surface is a single plate or a single layer of material (solid or porous) with a hard backing. The difference is significant when the surface consists of multilayers of solid or porous material and includes a layer of fluid with a large thickness relative to the other layers. The results are partially explained by considering the surface-reflection coefficients at the first-reflection angles.     

Affine registration: a comparison of several programs

Several registration programs with an affine model for the displacement field were tested on various 2D and 3D MRI of the same modality. The following programs were considered: AIR 3.0 (Woods, J. Comp. Assist. Tomogr, 22(1): 139-152, 1998), COCGV (Ostuni, JMRI, 7(2): 410-415, 1997), FLIRT (Jenkinson, Med. Image Analysis, 5(2): 143-156, 2001), Intramodal Registration (Thevenaz, IEEE Trans. Image Proc., 7(1): 27-41, 1998), SPM (Friston, Human Brain Mapping, 2: 165-189, 1995), and Patch Algorithm (Zhilkin, MRI 18(9): 1143-1150, 2000). Although some of these programs can perform multimodal registration, none was used in such a mode. This paper attempts a fair comparison of the performance of the Patch Algorithm with other programs. However, different settings of the programs' parameters may further improve the quality of the registration and/or change execution speed. The registered images, the CPU time required to perform the registration, and the error between the registered and reference images, are presented. Most of the programs give comparable accuracies of registration, but their execution times vary considerably. In general the AIR and Patch Algorithm require the least time. The Patch Algorithm can be easily parallelizable on a multi-processor computer.