Mass transport in a micro flow-through vial of a junction-at-the-tip capillary electrophoresis-mass spectrometry interface

When coupling capillary electrophoresis with postcolumn detection methods, such as mass spectrometry, the presence of postcolumn band broadening must be considered. The band broadening effects introduced by junction-at-the-tip CE-MS interfaces using a postcolumn micro flow-through vial are investigated by studying the hydrodynamic flow patterns and mass transport process inside the micro vial at the end of the CE separation capillary. Simulation results obtained by solving the Navier-Stokes and mass balance equations provide insights into the velocity field and concentration distribution of the analytes in the micro vial and demonstrate that, with a low flow rate of chemical modifier solution, the laminar flow streams confine the analyte molecules to the central part of the micro vial and thus maintain major features of the peak shapes. Peaks detected by UV and MS under similar experimental conditions were compared to verify the numerical prediction that the main features of the UV peak can be retained in the MS peak. Experiments also show that band broadening can be minimized when an appropriate chemical modifier flow rate is selected.     

Thermal Degradation Behavior and Product Speciation in Model Poly(dimethylsiloxane) Networks

The thermal degradation behavior of a series of well defined poly(dimethylsiloxane) (PDMS) model networks has been studied using a combination analytical thermal analysis techniques and multivariate statistical analysis in order to probe the influence of network architecture on degradation chemistry. The aim of this research has been to determine the effect differing network architectures: mono and bimodality, a range of crosslink density, inter-chain molar mass and percentage of free chain ends on the mechanisms of PDMS thermal degradation. A series of model PDMS networks have been formulated using of tin catalyzed condensation cure chemistry and a range of linear precursors to yield a matrix of model network systems. The thermal degradation chemistry of these model networks have been characterized in relation to their structure by means of pyrolysis gas chromatography mass spectrometry (Py-GCMS), thermal gravimetric analysis (TGA) and multivariate statistical analysis. The results clearly demonstrate that the structural architecture of (chemically similar) PDMS networks has a significant impact on the mechanisms of PDMS thermal degradation. Notability, with decreasing inter-crosslink chain length, larger cyclic siloxane species (>D5) become more abundant degradation products and that there is a relationship between inter-chain molar mass, degree of crosslinking and the thermal stability on the mechanisms of degradation. This work effectively demonstrates that quantifiable relationships exist between basic network architectures and the distributions of degradation derived species in PDMS networks.     

Statistical process control application to weld process

A statistical weld process monitoring system is described. Using data collected while welding, the welding statistical process control (SPC) tool provides weld process quality control by implementing techniques of data trending analysis, tolerance analysis, and sequential analysis. The SPC system computes the mean, standard deviation, and range of each of the parameters sampled by the data collection system. Changes in the mean, standard deviation, and range are displayed using control (or trend) charts. The control chart displays a function of a parameter with respect to the ordering of the weld records (for a single weld) or weld number (for multiple welds). The SPC tool also permits plotting tolerance charts of the mean, standard deviation, and range for each of the sampled parameters. The tolerance chart is plotted versus the record number (or weld number) and consists of a vertical line for each record (or weld number) showing the minimum and maximum value of that parameter for that record (or weld number). The upper control limit (UCL), lower control limit (LCL), and nominal value may also be displayed on the tolerance chart printout. The SPC also performs sequential analysis, which allows the user to examine the process as it goes along, which in turn may permit the user to locate a possible change in the process before it goes out of control. Work directed toward developing an expert interpreter of the voluminous statistical output generated by the SPC is also described     

The Influence of Polyhedral Oligomeric Silsequioxanes on Domain Microstructure in Polyurethane Elastomers

The influence of polyhedral oligomeric silsequioxanes (POSS) as covalently bound hybrid physical property modifiers on the segmental dynamics and morphology of segmented polyurethane elastomers has been studied by solid-state magic sandwich echo nuclear magnetic resonance (MSE-NMR), differential scanning calorimetry (DSC) and atomic force microscopy (AFM). A model system has been synthesized which incorporates diol functionalized POSS over a range of loadings into the hard-block of a methylene di-isocyanate - butane diol - poly(tetramethylene glycol) (MDI-BDO-PTMG) segmented PU elastomer. MSE-NMR has been employed to probe the segmental dynamics of the PU system as a function of POSS loading and it has been demonstrated that low levels of POSS as a substitute chain extender, both rigidify the hard-block phase of the PU and significantly alter both the phase morphology, mixing and structure of the inter-phase domains. These observations are supported by more classical AFM and DSC morphological characterization of the POSS-PU hybrid systems which show significant re-structuring of the phase domain structure of the PU and ordering of the crystalline hard-block domains. This work demonstrates the application of a multi-scaled experimental approach towards understanding the effects of three-dimensional, nano-scale cage moieties on the already complex phase structure of segmented polyurethanes. Through these efforts, new insight has been gained into the mechanisms by which low levels of a nano-material such as a cubic sesquioxane, can impact the phase separation and segmental dynamics of block ter-polymer polyurethanes.     

Trance logic as incomplete responding.

Two experiments tested predictions derived from the logical incongruity and differential demands hypotheses of trance logic responding. In Exp I, Ss that were highly susceptible to hypnosis showed higher levels of responding on 3 trance logic indexes (i.e., transparent hallucinating, duality, incongruous writing in age regression) than did Ss low in susceptibility to hypnosis who were instructed to fake hypnosis (i.e., simulators). In line with the differential demands hypothesis, hypnotic "reals" were less likely than simulators to report believing in the reality of the suggested situations and were less likely to report fine details in their hallucinations. Rate of trance logic responding correlated negatively with the degree to which hypnotic reals rated themselves as subjectively experiencing suggested effects, and as becoming absorbed in suggestions. Exp II found that highly susceptible hypnotic and nonhypnotic Ss (collectively called "reals") responded equivalently on all suggestions. High- and low-susceptible simulators also performed equivalently on all suggestions. Consistent with the differential demands hypothesis, (a) trance logic indexes differentiated reals from simulators when these indexes also measured incomplete subjective responding, and (b) trance logic indexes that failed to measure incomplete responding also failed to differentiate reals from simulators. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Amplification of the effectiveness of acetylcholinesterase for detoxification of organophosphorus compounds by bis-quaternary oximes

Pretreatment of rhesus monkeys with fetal bovine serum acetylcholinesterase (FBS AChE) provides complete protection against 5 LD50 of organophosphate (OP) without any signs of toxicity or performance decrements as measured by serial probe recognition tests or primate equilibrium platform performance (Maxwell et al., Toxicol Appl Pharmacol 115: 44-49, 1992; Wolfe et al., Toxicol Appl Pharmacol 117: 189-193, 1992). Although such use of enzyme as a single pretreatment drug for OP toxicity is sufficient to provide complete protection, a relatively large (stoichiometric) amount of enzyme was required in vivo to neutralize OP. To improve the efficacy of cholinesterases as pretreatment drugs, we have developed an approach in which the catalytic activity of OP-inhibited FBS AChE was rapidly and continuously restored, thus detoxifying the OP and minimizing enzyme aging by having sufficient amounts of appropriate oxime present. The efficacy of FBS AChE to detoxify several OPs was amplified by addition of bis-quaternary oximes, particularly 1-(2-hydroxyiminomethyl-1-pyridinium)-1-(4-carboxyaminopyridinium) -dimethyl ether hydrochloride (HI-6). When mice were pretreated with sufficient amounts of FBS AChE and HI-6 and challenged with repeated doses of O-isopropyl methylphosphonofluridate (sarin), the OP was continuously detoxified so long as the molar concentration of the sarin dose was less than the molar concentration of AChE in circulation. The in vitro experiments showed that the stoichiometry of sarin:FBS AChE was higher than 3200:1 and in vivo stoichiometry with mice was as high as 57:1. Addition of HI-6 to FBS AChE as a pretreatment drug amplified the efficacy of enzyme as a scavenger of nerve agents.