A ToF-MS with a Highly Efficient Electrostatic Ion Guide for Characterization of Ionic Liquid Electrospray Sources

We report on the development of a time-of-flight (ToF) mass spectrometer with a highly efficient electrostatic ion guide for enhancing detectability in ToF mass spectrometry. This 65-cm long ion guide consists of 13 cascaded stages of Einzel lens to collect a large fraction of emitted charges over a wide emission angle and energy spread for time-of-flight measurements. Simulations show that the ion guide can collect 100% of the charges with up to 23° emission half-angle or 30% energy spread irrespective of their specific charge. We demonstrate this ion guide as applied to electrospray ion sources. Experiments performed with tungsten needle electrospraying the ionic liquid EMI-BF₄ showed that up to 80% of the emitted charges could be collected at the end of the flight tube. Flight times of monomers and dimers emitted from the needles were measured in both positive and negative emission polarities. The setup was also used to characterize the electrospray from microfabricated silicon capillary emitters and nearly 30% charges could be collected even from a 40^° emission half-angle. This setup can thus increase the fraction of charge collection for ToF measurement and spray characteristics can be obtained from a very large fraction of the emission in real time.      

Electron capture detector response and dissociative electron attachment cross sections in chloroalkanes and chloroalkenes

Electron capture detectors (ECDs) are widely used in gas chromatography to detect electronegative compounds. In this work, we examine the connections between the ECD response and the cross sections for dissociative electron attachment (DEA) determined from low energy electron beam studies in the chloroalkane family, stressing in particular the role of temporary anion state energies. We show that attachment rate coefficients computed from these cross sections are well correlated with ECD response, and that the latter decreases exponentially with increasing energies of the lowest anion states. ECD measurements are also carried out in monochloroalkanes substituted with unsaturated ethenyl and phenyl moieties, and the response is shown to depend strongly on the mixing between the unsaturated pi* and the C-Cl sigma* temporary anions as exhibited by the vertical attachment energies (VAEs) of these states. The results show good correlations between the chloroalkene and phenyl chloride ECD responses and the VAEs for the mixed states.     

Finitary isomorphism of some renewal processes to Bernoulli schemes

Using the marker and filler methods of Keane and Smorodinsky, we prove that entropy is a complete finitary isomorphism invariant for r-processes. It is conjectured that entropy is a complete finitary isomorphism invariant for finitary factors of Bernoulli schemes. We present a weaker version of this conjecture with hope that its proof is more attainable with present methods. In doing so, we define a one-way finitary isomorphism and prove one-way finitary results for random walks. We will also extend the marker and filler methods of Keane and Smorodinsky to a class of countable state processes.     

Characterization of the effects of compressed gas annealing on semicrystalline polymers

The effects of annealing semicrystalline polymers in the presence of plasticizing agents is an area of considerable current interest, given the potential to modify the degree and nature of crystallinity. These effects were studied for two semicrystalline polymers, custom‐synthesized methyl‐substituted poly(aryl ether ether ketone) (MePEEK) and industrial‐grade poly(ethylene terephthalate) (PET). Small‐angle X‐ray scattering (SAXS) was used to characterize the microstructure of both amorphous and preannealed materials. Differential scanning calorimetry (DSC), wide‐angle X‐ray scattering, and density measurements were also performed for the PET samples, and reference is made to similar analysis work done for MePEEK. A distinct morphological effect could be identified from SAXS measurements of MePEEK annealed in a stepwise fashion in the presence of high‐pressure CO₂ with the polar cosolvent CH₃OH. This result was absent in MePEEK similarly annealed in air and supports earlier DSC measurements. A very different morphological effect of pressure alone was observed in PET annealed in pure CO₂ (170 and 510 atm) at a temperature of 150 °C, well above the glass transition. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2457–2467, 2000     

The surface marker and micro cell method

A new method is presented for the simulation of two-dimensional, incompressible, free surface fluid flow problems. The surface marker and micro cell (SMMC) method is capable of simulating transient free surface fluid flow problems that include multivalued free surfaces, impact of free surfaces with solid obstacles and converging fluid fronts (including wave breaking). New approaches are presented for the advection of the free surface, the calculation of the tentative velocity, final velocity and pressure fields and the use of multivalued velocities to treat converging fluid fronts. Simulation results are compared with experimental results for water sloshing in a tank to demonstrate the validity of the new method. Convergence of the new method is demonstrated by a grid refinement study. © 1997 John Wiley & Sons, Ltd.     

Special Issue: International Symposium on Mathematical Programming 2022

Mathematical Programming -     

On-chip dielectrophoretic recovery and detection of a lactate sensing probiotic from model human saliva

Early detection has led to increased survival for multiple cancers; however, the 5-year survival rate of oral carcinoma (OC) has remained at 40% for the last several decades. Screening for OC is routinely done via visual examinations, followed by tissue biopsy and laboratory testing. Point-of-care testing would be a more convenient and widely available alternative for at-risk individuals. Increased lactate production is a hallmark of many head-and-neck tumors, due to the Warburg Effect, where tumor cells favor glycolysis in the place of oxidative phosphorylation. To detect excess lactate, we have modified the commensal bacterium Escherichia coli Nissle 1917 to express fluorescent reporter genes in response to extracellular lactate. Administering this commensal as a mouth wash and subsequently collecting saliva for the detection of the reporter may allow for noninvasive, early detection of cancerous lesions in at-risk individuals. Furthermore, we demonstrate a new on-chip electrokinetic technique to recover these probiotic probes from model saliva fluid to improve the detection of reporter gene activation.