The Synthesis of Phosphonate Ester Containing Fluorinated Vinyl Ethers

Three novel perfluorovinyl ethers containing phosphonate ester groups, diethyl 1,1,2,2,3,3,5,6,6-nonafluoro-4-oxa-5-hexenylphosphonate, (EtO)(2)P(O)(CF(2))(3)OCF=CF(2) (1), diethyl 1,1,2,2,4,5,5-heptafluoro-3-oxa-4-pentenylphosphonate, (EtO)(2)P(O)(CF(2))(2)OCF=CF(2) (2), and diethyl 1,1,2,2,4,5,5,7,8,8-decafluoro-4-trifluoromethyl-3,6-dioxa-7-octenylphosphonate, CF(2)=CFOCF(2)CF(CF(3))O(CF(2))(2)P(O)(OEt)(2) (3), have been synthesized. Perfluorovinyl ethers 1 and 2 were synthesized from methyl 4-trifluoroethenoxy-2,2,3,3,4,4-hexafluorobutanoate and methyl 3-trifluoroethenoxy-2,2,3,3-tetrafluoropropanoate, respectively, while perfluorovinyl ether 3 was synthesized either from 5-trifluoroethenoxy-4-trifluoromethyl-3-oxa-1,1,2,2,4,5,5-heptafluoropentylsulfonyl fluoride or methyl 6-trifluoroethenoxy-5-trifluoromethyl-4-oxa-2,2,3,3,5,6,6-heptafluorohexanoate. The carboxylate esters were converted to the corresponding fluoroalkyl iodides via a free-radical iododecarboxylation. The sulfonyl fluoride was converted to its corresponding fluoroalkyl iodide via iododesulfination. The intermediate iodides were found to be useful precursors for the incorporation of the phosphonic ester groups via a photoreaction with tetraethyl pyrophosphite to produce diethyl fluorophosphonites. The diethyl fluorophosphonites were oxidized to the desired phosphonates, 1, 2, and 3, utilizing hydrogen peroxide as the oxidant. Moderate to good overall yields of perfluorovinyl ethers 1-3 have been achieved.     

31P Solid state NMR study of structure and chemical stability of dichlorotriphenylphosphorane

Solid state ³¹P NMR spectroscopy was used to examine, monitor and quantify the compound integrity of the chemical reagent dichlorotriphenylphosphorane. Comparison was also made with solution ³¹P NMR spectra which showed that this highly reactive species could be observed in dry benzene prior to conversion to the hydrolyzed product. This is the first reported solid state NMR study of the stability and reactivity of dichlorotriphenylphosphorane and the first account of its observation and comparison in the solution state. In the solid state, the ionic and covalent forms for dichlorotriphenylphosphorane were observed along with hydrolyzed products, however, the degree of hydrolysis was dependent upon the rotor packing conditions. Calculation of the relative percent composition of dichlorotriphenylphosphorane with hydrolyzed product was made for samples prepared in air versus under nitrogen atmosphere. This information was critical in adjusting the amount of reagent used in chemical development syntheses and scale up laboratories. All hydrolyzed products were identified, based upon chemical comparisons with spectra of pure materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Open- and closed-loop aberration correction by use of a quadrature interferometric wave-front sensor

Experimental results are presented for an adaptive optics system based on a quadrature Twyman-Green interferometric wave-front sensor. The system uses a circularly polarized reference beam to form two interferograms with a pi/2 phase shift. The experiments conducted used Kolmogorov phase screens to simulate atmospheric phase distortions. Strehl ratio improvements by a factor of 8, to an absolute value of 0.45, are demonstrated.     

Chelating ligand alters the microscopic mechanism of mineral dissolution

Ethylenediamine tetraacetate (EDTA)-mediated calcite dissolution occurs via a different process than water-promoted dissolution. Near-atomic-scale observations in EDTA solutions demonstrate that, after penetration through a critical pit depth barrier, step velocity increases linearly with pit depth for EDTA-promoted dissolution. The parallel processes of water-dominated dissolution at point defects and ligand-dominated dissolution at linear defects are clearly observable in real-time atomic force micrographs. EDTA and water initiate and propagate dissolution steps with pit-depth-dependent and -independent step velocities, respectively. The linear defects are susceptible to continuously increasing step velocities, but the point defects are not. The findings update the conceptual framework of the microscopic mechanism of mineral dissolution.     

Backscattering of transients by tilted truncated cylindrical shells: time-frequency identification of ray contributions from measurements

Impulse backscattering measurements by a thick-walled finite cylindrical shell are examined in the time-frequency domain to identify and characterize individual ray contributions from generalized Lamb waves excited on the shell. Previous experiments and analysis in the frequency-aspect angle domain [S. F. Morse et al., J. Acoust. Soc. Am. 103, 785-794 (1998)] indicate that large backscattering enhancements occur in the midfrequency region for the shell tilted at large angles. Presently this experimental data is examined in the time-frequency domain for selected angles of incidence. Individual ray contributions are evident and their evolution over aspect angle is discussed. The most prominent contribution is due to the meridional ray of the a0 leaky Lamb wave. This feature distinctly highlights the truncation of the shell and is found over a range of aspect angles spanning 200 degrees for the frequencies examined. Also observed are periodic features corresponding to end-reflected helical waves of the a0-. These scattering features are significantly different from those reported for thin-walled finite cylinders at low frequencies. The present results may be useful for target identification and localization and as a comparison tool for high-frequency computational scattering models.     

A practical approach to the synthesis of 2,4-disubstituted oxazoles from amino acids

[reaction: see text] A new sequence for the synthesis of various 2,4-disubstituted oxazoles from alpha-amino acids is reported. The method is shown to be general and incorporates the reagent combination, triphenylphosphine/hexachloroethane, for cyclodehydration of intermediate alpha-acylamino aldehydes. Implementation of this reagent system for the conversion of alpha-acylamino ketones to oxazoles is briefly investigated.     

Measuring One Aspect of Teachers’ Affective States: Development of the Science Teachers’ Pedagogical Discontentment Scale

The aim of this research is to describe the development of the Science Teachers’ Pedagogical Discontentment Scale, an instrument that measures the discontentment that arises in teachers as they recognize a mismatch between their own pedagogical beliefs and goals and their actual classroom practices. From a conceptual change perspective, we explore the meaning of pedagogical discontentment and discuss its role in shaping teachers’ receptivity to messages of reform. We present an instrument that can be used to measure teachers’ pedagogical discontentment, an instrument that will allow science educators to better describe the affective states of teachers as they enter professional development experiences. The items for the initial instrument were derived from a series of interviews with practicing teachers; from these interviews, a group of 42 items were designed around a group of five subscales. The final instrument, revised after two rounds of field testing, includes 21 multiple‐choice items clustered around six subscales (subscales derived from interviews with science teachers). The processes used to develop the items and to refine instrument are discussed. Uses for this instrument to inform professional development experiences are explored as well as implications.     

Effect of tethered and free microfibrillated cellulose (MFC) on the properties of paper composites

High strength and low gas permeability cellulosic composites were produced using the papermaking technology with a commercial microfibrillated cellulose (MFC). The effect of blending MFC with hardwood fibers was compared to the direct refining of the fibers with and without polyamideamine-epichlorohydrin (PAE) addition. The addition of MFC, free or tethered, to pulp fibers combined with PAE can increase the dry strength and wet strength of cellulosic materials by an order of magnitude. Air permeability of the composites decreases by up to orders four of magnitude with MFC addition. The hypothesis that refining wood fibers can produce tethered MFC which provides equivalent strength properties but significant drainage benefits was proven. Furthermore, major benefits in paper formation uniformity (fiber distribution homogeneity) were achieved with refined fibers.     

Approximation of an open polygonal curve with a minimum number of circular arcs and biarcs

We present an algorithm for approximating a given open polygonal curve with a minimum number of circular arcs. In computer-aided manufacturing environments, the paths of cutting tools are usually described with circular arcs and straight line segments. Greedy algorithms for approximating a polygonal curve with curves of higher order can be found in the literature. Without theoretical bounds it is difficult to say anything about the quality of these algorithms. We present an algorithm which finds a series of circular arcs that approximate the polygonal curve while remaining within a given tolerance region. This series contains the minimum number of arcs of any such series. Our algorithm takes O(n²logn) time for an original polygonal chain with n vertices. Using a similar approach, we design an algorithm with a runtime of O(n²logn), for computing a tangent-continuous approximation with the minimum number of biarcs, for a sequence of points with given tangent directions.     

Cloud condensation nuclei (CCN) activity and oxygen-to-carbon elemental ratios following thermodenuder treatment of organic particles grown by α-pinene ozonolysis

The effects of thermodenuder treatment on the cloud condensation nuclei (CCN) activity and elemental composition of organic particles grown by α-pinene ozonolysis were investigated. The secondary organic material (SOM) was produced in a continuous-flow chamber, with steady-state organic particle mass concentrations M(org) ranging from 1.4 to 37 μg m(-3). Particles exiting in the outflow were heated to temperatures T of up to 100 °C in a thermodenuder. The oxygen-to-carbon (O:C) and hydrogen-to-carbon (H:C) ratios were measured by on-line mass spectrometry. The observed elemental ratios were fit by a linear function, given by (H:C) = -0.8 (O:C) +1.8 for 0.38 < O:C < 0.50. This fit included the dependence on both M(org) and T, meaning that the single variable of post-thermodenuder M(org) was sufficient as an accurate predictor for O:C(M(org)(T)) and H:C(M(org)(T)). This result suggests that equilibrium partitioning theory largely governed the initial volatilization in the thermodenuder. By comparison, the CCN activity had a different dependence on thermodenuder treatment. At 25 °C, the CCN activity was independent of M(org), having an effective hygroscopicity parameter κ(org) of 0.103 ± 0.002. At 100 °C, however, κ(org) varied from 0.105 for M(org) = 1.4 μg m(-3) to 0.079 for M(org) = 37 μg m(-3), indicating that for high mass concentration the CCN activity decreased with heat treatment. The interpretation is that the oligomer fraction of the SOM increased at elevated T, both because of particle-phase reactions that produced oligomers under those conditions and because of the relative enrichment of lower-volatility oligomers in the SOM accompanying the evaporation of higher-volatility monomers from the SOM. Oligomers have high effective molecular weights and thereby significantly influence CCN activity. The production rates of different types of oligomers depend on the types and concentrations of functional groups present in the SOM, which in turn are strongly influenced by M(org). We conclude with a hypothesis, which is supported by a detailed molecular kinetic model, that the changes in κ(org) at high T were more significant at high compared to low M(org) because particle-phase SOM at high M(org) contained a mix of functional groups favorable to oligomerization, such as carbonyl groups.