Radio-Frequency Hexamethyldisiloxane Plasma Deposition: A Comparison of Plasma- and Deposit-Chemistry

This study reports on the effect of input power to hexamethyldisiloxane (HMDSO) plasmas. The power dependence of the plasma-phase species and of the surface chemistry (of the deposits) has been investigated. Neutral and positive molecular species were detected within the plasma using mass spectrometry (MS). Secondary ion mass spectrometry (SIMS) was used to probe the molecular structure of the deposits. The elemental composition of the surface was determined by XPS and the deposition rate was monitored using a vibrating quartz crystal microbalance. Neutral and cationic molecules of mass greater than HMDSO were detected in the plasma. Their formation through ion-molecule reactions is proposed. Changes in the relative concentration of plasma-phase species follow those seen in molecular species detected at the deposit surface. Thus, we believe that the molecular structure of the deposits can be related to the species present in the plasma. While traditionally the dominant mechanism in deposit formation is assumed to be free radical combinations, we propose other possibilities involving cations with the aim of putting forward a new perspective on plasma polymerization mechanisms and thereby stimulating discussion.     

Automated derivatization for on-line solid-phase extraction-gas chromatography; phenolic compounds

An automated system for derivaatization was coupled on-line with solid-phase extraction-gas-chromatography (SPE-GC). The system was optimized for the determination of phenol and chlorinated phenols in aqueous samples. The test analytes were acetylated with acetic anhydride; proper buffering of the sample was a critical factor. Next, the phenol acetates were enriched on a SPE cartridge and transferred to a GC; two appraoaches were studied. In the first approach, the derivatives were enriched on disposable C18 cartridges (ASPEC type) and desorbed with methylacetate. Aan aliquot of the final eluate was injected on-line the GC by means of a loop-type interface. In the second approach, trace enrichment was performed on 10 × 2 mm i.d. LC-type precolumn packed with polystyrenedivinylbenzene copolymer (PLRP-S) this precolumn was dried with a mitrogen purge and the phenol acetates were desorbed with ethyl acetate which was injectedon-line into the retention gap of the GC under partially concurrent solvent evaporation (PCSE) conditions. The Derivatization-SPE-GC system which was based on the loop-type interface has the advantage of simplicity and easy operation, the main drawback is the impossibility to determine phenol acetates which elute prior to trichlorophenol acetates. With the derivatization-SPE-GC approach using PCSE-based desorption, even the most volatile analyte of the test series, phenol acetate, can be determined successfully. The entire procedure, including the derivatization step, was fully automated and integrated in one set-up. The precision data for the integrated on-line derivatization-SP-FID system were fully satisfactory, with RSD values of 1–12 % at the 1 μg/1 level. When a sample volume of 2.2 ml was analyzed, The detection limits for the chlorinated phenol acetates were in the 0.1–0.3 μg/1 range.     

A comparison of239+240Pu post-mortem measurements with estimates based on current ICRP models

Measurements of^239+240Pu in human tissues, from nuclear weapons testing, provide an invaluable source of data for verifying the uptake and distribution of radionuclides in the body. Measured concentrations of^239+240Pu in lung, tracheobronchial lymph nodes, liver and skeleton have been compared with concentrations calculated using estimated plutonium intakes, the ICRP Publication 66 Respiratory Tract Model and the ICRP Publication 67 biokinetic model for plutonium. Measurement data tend to fall between the concentrations estimated on the basis of Type M and Type S absorption parameters. This indicates that the models represent the movement of plutonium through the body reasonably well.     

Modeling synchronization and suppression of spontaneous otoacoustic emissions using Van der Pol oscillators: effects of aspirin administration

Many of the aspects of the interaction of spontaneous otoacoustic emissions with external tones (suppression and synchronization) can be qualitatively simulated by the behavior of a single driven Van der Pol oscillator. Analytical and numerical investigations of a model of spontaneous otoacoustic emissions based on such an oscillator (with appropriate parametric changes in the nonlinear and negative damping components) lead to predictions of the nature of the changes in suppression and synchronization (frequency-locking) tuning curves when the levels of spontaneous otoacoustic emissions are modified. Observations of the suppression and synchronization of spontaneous otoacoustic emissions by external tones of different frequencies and levels were obtained while the levels of spontaneous emissions were altered by aspirin administration. Modeling an emission as a single Van der Pol oscillator qualitatively accounts for: (1) the reduction of the level of an external tone required to suppress the emission by a decibel amount equivalent to the level reduction induced by aspirin administration; (2) the broadening of the frequency-locking tuning curve of an emission whose level is reduced; and (3) the pulling of the emission frequency by an external tone. It does not account for: (1) the observed asymmetry in the slopes of the external-tone suppression curves (more gradual for frequencies of the suppressor tone higher, rather than lower, than that of the emission); and (2) the frequency pushing of the emission by an external tone.     

Crutch or Catalyst: Teachers' Beliefs and Practices Regarding Calculator use in Mathematics Instruction

This study investigated K‐12 teachers' beliefs and reported teaching practices regarding calculator use in their mathematics instruction. A survey was administered to more than 800 elementary, middle and high school teachers in a large metropolitan area to address the following questions: (a) what are the beliefs and practices of mathematics teachers regarding calculator use? and (b) how do these beliefs and practices differ among teachers in three grade bands? Factor analysis of 20 Likert scale items revealed four factors that accounted for 54% of the variance in the ratings. These factors were named Catalyst Beliefs, Teacher Knowledge, Crutch Beliefs, and Teacher Practices. Compared to elementary teachers, high school teachers were significantly higher in their perception of calculator use as a catalyst in mathematics instruction. However, the higher the grade level of the teacher, the higher the mean score on the perception that calculator use may be a way of getting answers without understanding mathematical processes. The mean scores for teachers in all three grade bands indicated agreement that students can learn mathematics through calculator use and using calculators in instruction will lead to better student understanding and make mathematics more interesting. The survey results shed light on teachers' self reported beliefs, knowledge, and practices in regard to consistency with elements of the National Council of Teachers of Mathematics Principles and Standards for School Mathematics (2000) technology principle and the NCTM use of technology position paper (2003). This study extended previous research on teachers' beliefs regarding calculator use in classrooms by examining and comparing the results of teacher surveys across three grade bands.     

Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Photocrosslinked poly(vinylbenzophenone)‐core micelles via mild Friedel–Crafts benzoylation of polystyrene amphiphiles

Photocrosslinkable poly(vinylbenzophenone)‐containing polymers were synthesized via a one‐step, Friedel–Crafts benzoylation of polystyrene‐containing starting materials [including polystyrene, polystyrene‐block‐poly(tert‐butyl acrylate), polystyrene‐block‐poly(ethylene oxide), polystyrene‐block‐poly(methyl methacrylate), and polystyrene‐block‐poly(n‐butyl acrylate)] with benzoyl trifluoromethanesulfonate as a benzoylation reagent. The use of this mild reagent (which required no added Lewis acid) permitted polymers with well‐defined compositions and narrow molecular weight distributions to be synthesized. Micelles formed from one of these benzoylated polymers, [polystyrene_0.25‐co‐poly(vinylbenzophenone)_0.75]₁₁₅‐block‐poly(acrylic acid)₁₄, were then fixed by the irradiation of the micelle cores with UV light. As the irradiation time was increased, the pendent benzophenone groups crosslinked with other chains in the glassy micelle cores. Dynamic light scattering, spectrofluorimetry, and Fourier transform infrared spectroscopy were all used to verify the progress of the crosslinking reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2604–2614, 2006     

SPAR: stochastic programming with adversarial recourse

We consider a general adversarial stochastic optimization model. Our model involves the design of a system that an adversary may subsequently attempt to destroy or degrade. We introduce SPAR, which utilizes mixed-integer programming for the design decision and a Markov decision process (MDP) for the modeling of our adversarial phase.