The stress cracking of polyamides by metal salts. Part III. Metal thiocyanates

The stress cracking of polyamide (nylon 6) by a number of metal thiocyanates in aqueous and nonaqueous solutions has been investigated. Lithium, zinc and cobalt_II thiocyanates were the most active and their activity was compared with that of the corresponding metal halides. Stress cracking parameters were determined and the mechanism of cracking studied by infrared techniques. The action of metal thiocyanates on nylon 6 is similar to that of the corresponding metal halides. Some metal cobaltothiocyanates were also found to be active stress cracking agents.     

Molecular modelling of Staphylococcal {delta}-toxin ion channels by restrained molecular dynamics

-Toxin is a 26-residue channel-forming peptide from Staphylococcusaureus which forms an amphipathic -helix in a membrane environment.Channel formation in planar bilayers suggests that an averageof six -toxin helices self-assemble to form transbilayer pores.Molecular models for channels formed by -toxin and by a syntheticanalogue have been generated using a simulated annealing protocolapplied via restrained molecular dynamics. These models areanalysed in terms of the predicted geometric and energetic propertiesof the transbilayer pores. Pore radius calculations of the modelsdemonstrate that rings of channel-lining residues contributea series of constrictions along the pore. Electrostatic propertiesof the pores are determined both by pore-lining charged sidechains and by the aligned helix dipoles of the parallel helixbundle. Molecular dynamics simulations (100 ps) of -toxin modelscontaining intra-pore water were performed. Analysis of theresultant dynamics trajectories further supports the proposalthat alternative conformations of pore-constricting side chainsmay be responsible for the observed conductance heterogeneityof -toxin ion channels.     

Guanine and plasmid DNA binding of mono- and trinuclear fac-[Re(CO)3]+ complexes with amino acid ligands

We have synthesized and fully characterized four new complexes comprising the fac-[Re(CO)3]+ moiety and the ligands NH3, L-proline (Pro), or N,N-dimethylglycine (dmGly). The reaction of [Re(H2O)3(CO)3]+ with the two amino acids gives trinuclear complexes of general formula [Re(L)(CO)3]3 (where L = amino acid). We have studied the in vitro behavior of these compounds with guanine and DNA in order to understand whether the cytotoxicity exhibited by certain rhenium complexes based on the fac-[Re(CO)3]+ core is due to the formation of nucleobase complexes and inter- or intrastrand links between DNA bases. We have performed model studies with guanine and studied the structural effects induced by different rhenium(I) tricarbonyl complexes on PhiX174 plasmid DNA by electrophoretic methods. Our results show that rhenium complexes with two available coordination sites interact with plasmid DNA to form a stable adduct that is likely to involve two bases.     

Characterization of chemicals mediating ovipositional host-plant finding byAmyelois transitella females

Ovipositional host-finding in the navel orangeworm,Amyelois transitella (Walker), is brought about by an in-flight response to host odors. Wind-tunnel studies of the response of gravid females to almonds showed that this response is mediated primarily by long-chain fatty acids, particularly oleic acid and linoleic acid. Evidence for the behavioral activity of fatty acids is based on the fact that: (1) behavioral activity of almond oil was concentrated in a single liquid chromatographic fraction whose composition was predominantly long-chain fatty acids, (2) behavioral activity was lost when either almond oil or the active fraction of that oil was treated with diazomethane, (3) full activity was elicited by a selective extraction of free fatty acids from crude almond oil, and (4) upwind response by females was elicited by a blend of synthetic oleic and linoleic acids, albeit at a level less than that elicited by almond oil. Five fatty acids identified from the almond oil were: myristic acid (1%), palmitic acid (16%), stearic acid (3%), oleic acid (58%), and linoleic (22%). Attraction to various combinations of synthetic acids was observed only when oleic acid was present, and oleic acid elicited upwind flights to the source when presented alone; however, short-range responses were enhanced by the addition of linoleic acid, which elicited no long-range orientation by itself. Despite significant levels of attraction to synthetic blends, the percentage of females flying to the source was lower than that flying to acidulated almond oil, the best natural attractant tested. Thus, although longrange response may be mediated primarily by a blend of oleic and linoleic acids, additional and as yet unidentified components must also play an important role. Long-range chemically modulated host finding in this and other generalist plant feeders is discussed with respect to current models of the evolution of host finding, and it is argued that suggestions that long-range host finding should be correlated with narrowness of host utilization are logically flawed and are not supported by our current understanding of specific examples of host finding.     

An NMR study of the dissociation of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate) and its crosslinking of polymers containing labile hydrogens. II

Nuclear magnetic resonance spectroscopy has been used to study the dissociation and reaction of N,N′-(2-propyloximino)-4,4′-methylenebis(phenylcarbamate), as a crosslinking agent for polymers containing labile hydrogens. The crosslinking of poly(acrylic acid), polyacrylamide, and poly(vinyl alcohol) was found to result upon heating each to 150°C for 10 min with this component at 2–10 wt %.     

Microstructure of high modulus solid state extruded polyethylene: 2. X-ray scattering studies of 12, 24 and 36 extrusion draw ratio

The microstructure of a series of solid state extruded polyethylene fibres was examined by wide- and small-angle X-ray scattering. By measuring absolute intensities using a two dimensional position sensitive detector, accurate values of the small-angle invariant for anisotropic samples were obtained. This measurement coupled with wide-angle X-ray scattering and d.s.c. permitted determination of the density of the noncrystalline component. The use of a two phase model for solid state extruded polyethylene is justified if consideration is given to the effective densities of the crystalline and noncrystalline phases, which change with deformation. The effective density of the crystalline phase decreases by 1% (0.999–0.990 g cm^?3) from the unextruded billet compared to a 36 draw ratio extrudate, while the noncrystalline phase density increases by 6% (0.84–0.89 g cm^?3). These changes lead to an overall decrease in the mean squared electron density fluctuation of 63%. The average axial crystallite length measured by wide-angle X-ray scattering increases with extrusion draw ratio while the SAXS long period decreases and weakens considerably. These observations and the electron microscopy results from the previous paper, (Polymer, 1982, 23, 1069), are fully consistent with the key features of the Peterlin model of fibre microstructure.     

Hydroisomerization of Renewable and Fossil n-Alkanes over Bifunctional Dealuminated ZSM-5 Catalysts

The hydroisomerization of two long-chain n-alkane mixtures was investigated over bifunctional Pt/H-ZSM-5 catalysts before and after dealumination of preshaped zeolite/binder pellets. The hydroisomerization over the dealuminated catalysts leads to more isomers and less cracking products. Consequently, higher ratios of multi- to mono-branched isomerization products are formed as expected for large- rather than medium-pore zeolites. This indicates a higher availability of space in the vicinity of the active sites and provides an attractive route to make medium-pore zeolites suitable for upgrading higher boiling hydrocarbon feeds.     

A gain and bandwidth enhanced transimpedance preamplifier for Fourier-transform ion cyclotron resonance mass spectrometry

The nature of the ion signal from a 12-T Fourier-transform ion cyclotron resonance mass spectrometer and the electronic noise were studied to further understand the electronic detection limit. At minimal cost, a new transimpedance preamplifier was designed, computer simulated, built, and tested. The preamplifier design pushes the electronic signal-to-noise performance at room temperature to the limit, because of its enhanced tolerance of the capacitance of the detection device, lower intrinsic noise, and larger flat mid-band gain (input current noise spectral density of around 1 pA/√Hz when the transimpedance is about 85 dBΩ). The designed preamplifier has a bandwidth of ~3 kHz to 10 MHz, which corresponds to the mass-to-charge ratio, m/z, of approximately 18 to 61 k at 12 T. The transimpedance and the bandwidth can be easily adjusted by changing the value of passive components. The feedback limitation of the circuit is discussed. With the maximum possible transimpedance of 5.3 MΩ when using an 0402 surface mount resistor, the preamplifier was estimated to be able to detect ~110 charges in a single scan.     

The diffusion decision model: theory and data for two-choice decision tasks

The diffusion decision model allows detailed explanations of behavior in two-choice discrimination tasks. In this article, the model is reviewed to show how it translates behavioral data-accuracy, mean response times, and response time distributions-into components of cognitive processing. Three experiments are used to illustrate experimental manipulations of three components: stimulus difficulty affects the quality of information on which a decision is based; instructions emphasizing either speed or accuracy affect the criterial amounts of information that a subject requires before initiating a response; and the relative proportions of the two stimuli affect biases in drift rate and starting point. The experiments also illustrate the strong constraints that ensure the model is empirically testable and potentially falsifiable. The broad range of applications of the model is also reviewed, including research in the domains of aging and neurophysiology.     

Learning traversability models for autonomous mobile vehicles

Autonomous mobile robots need to adapt their behavior to the terrain over which they drive, and to predict the traversability of the terrain so that they can effectively plan their paths. Such robots usually make use of a set of sensors to investigate the terrain around them and build up an internal representation that enables them to navigate. This paper addresses the question of how to use sensor data to learn properties of the environment and use this knowledge to predict which regions of the environment are traversable. The approach makes use of sensed information from range sensors (stereo or ladar), color cameras, and the vehicle’s navigation sensors. Models of terrain regions are learned from subsets of pixels that are selected by projection into a local occupancy grid. The models include color and texture as well as traversability information obtained from an analysis of the range data associated with the pixels. The models are learned without supervision, deriving their properties from the geometry and the appearance of the scene. The models are used to classify color images and assign traversability costs to regions. The classification does not use the range or position information, but only color images. Traversability determined during the model-building phase is stored in the models. This enables classification of regions beyond the range of stereo or ladar using the information in the color images. The paper describes how the models are constructed and maintained, how they are used to classify image regions, and how the system adapts to changing environments. Examples are shown from the implementation of this algorithm in the DARPA Learning Applied to Ground Robots (LAGR) program, and an evaluation of the algorithm against human-provided ground truth is presented.