A Tandem Enol Silane Formation-Mukaiyama Aldol Reaction Mediated by TMSOTf

A slight excess of silyl trifluoromethanesulfonate mediates a tandem enol silane formation-Mukaiyama aldol reaction in the presence of Hunig’s base. Preformation of the enol silane is unnecessary for efficient reactions, which proceed in 75–97% yield for the addition of aryl methyl ketones and acetate esters to non-enolizable aldehydes. Mechanistic data suggests that free amine is crucial for full conversion

One-Pot Enol Silane Formation-Mukaiyama Aldol-Type Addition to Dimethyl Acetals Mediated by TMSOTf

Various ketones, esters, amides, and thioesters add in high yield to dimethyl acetals in the presence of silyl trifluoromethanesulfonates and an amine base. Acetals derived from aryl, unsaturated, and aliphatic aldehydes are all effective substrates. The reaction proceeds in a single reaction flask, with no purification of the intermediate enol silane necessary

Moderate Resolution Spectroscopy For The Space Infrared Telescope Facility (SIRTF)

A conceptual design for an infrared spectrometer capable of both low resolution (λ/Δ-λ = 50; 2.5-200 microns) and moderate resolution (1000; 4-200 microns) and moderate resolution (1000; 4-200 microns) has been developed. This facility instrument will permit the spectroscopic study in the infrared of objects ranging from within the solar system to distant galaxies. The spectroscopic capability provided by this instrument for SIRTF will give astronomers orders of magnitude greater sensitivity for the study of faint objects than had been previously available. The low resolution mode will enable detailed studies of the continuum radiation. The moderate resolution mode of the instrument will permit studies of a wide range of problems, from the infrared spectral signatures of small outer solar system bodies such as Pluto and the satellites of the giant planets, to investigations of more luminous active galaxies and QS0s at substantially greater distances. A simple design concept has been developed for the spectrometer which supports the science investigation with practical cryogenic engineering. Operational flexibility is preserved with a minimum number of mechanisms. The five modules share a common aperture, and all gratings share a single scan mechanism. High reliability is achieved through use of flight-proven hardware concepts and redundancy. The design controls the heat load into the SIRTF cryogen, with all heat sources other than the detectors operating at 7K and isolated from the 4K cold station. Two-dimensional area detector arrays are used in the 2.5-120μm bands to simultaneously monitor adjacent regions in extended objects and to measure the background near point sources

Long term microparticle impact fluxes on LDEF determined from optical survey of Interplanetary Dust Experiment (IDE) sensors

Many of the IDE metal-oxide-silicon (MOS) capacitor-discharge impact sensors remained active during the entire Long Duration Exposure Facility (LDEF) mission. An optical survey of impact sites on the active surfaces of these sensors has been extended to include all sensors from the low-flux sides of LDEF (i.e. the west or trailing side, the earth end, and the space end) and 5-7 active sensors from each LDEF's high-flux sides (i.e. the east or leading side, the south side, and the north side). This survey was facilitated by the presence of a relatively large (greater than 50 micron diameter) optical signature associated with each impact site on the active sensor surfaces. Of the approximately 4700 impacts in the optical survey data set, 84% were from particles in the 0.5 to 3 micron size range. An estimate of the total number of hypervelocity impacts on LDEF from particles greater than 0.5 micron diameter yields a value of approximately 7 x 10(exp 6). Impact feature dimensions for several dozen large craters on MOS sensors and germanium witness plates are also presented. Impact fluxes calculated from the IDE survey data closely matched surveys of similar size impacts (greater than or equal to 3 micron diameter craters in Al, or marginal penetrations of a 2.4 micron thick Al foil) by other LDEF investigators. Since the first year IDE data were electronically recorded, the flux data could be divided into three long term time periods: the first year, the entire 5.8 year mission, and the intervening 4.8 years (by difference). The IDE data show that there was an order of magnitude decrease in the long term microparticle impact flux on the trailing side of LDEF, from 1.01 to 0.098 x 10(exp -4) m(exp 2)/s, from the first year in orbit compared to years 2-6. The long term flux on the leading edge showed an increase from 8.6 to 11.2 x 10(exp -4) m(exp -2)/s over this same time period. (Short term flux increases up to 10,000 times the background rate were recorded on the leading side during LDEF's first year in orbit.) The overall east/west ratio was 44, but during LDEF's first year in orbit the ratio was 8.5, and during years 2-6 the ratio was 114. Long term microparticle impact fluxes on the space end decreased from 1.12 to 0.55 x 10(exp -4) m(exp -2)/s from the first year in orbit compared to years 2-6. The earth end showed the opposite trend with an increase from 0.16 to 0.38 x 10(exp -4) m(exp -2)/s. Fluxes on rows 6 and 12 decreased from 6.1 to 3.4 and 6.7 to 3.7 x 10(exp -4) m(exp -2)/s, respectively, over the same time periods. This resulted in space/earth microparticle impact flux ratios of 7.1 during the first year and 1.5 during years 2-6, while the south/north, space/north and space/south ratios remained constant at 1.1, 0.16 and 0.17, respectively, during the entire mission. This information indicates the possible identification of long term changes in discrete microparticle orbital debris component contributions to the total impact flux experienced by LDEF. A dramatic decrease in the debris population capable of striking the trailing side was detected that could possibly be attributed to the hiatus of western launch activity experienced from 1986-1989. A significant increase in the debris population that preferentially struck the leading side was also observed and could possibly be attributed to a single breakup event that occurred in September of 1986. A substantial increase in the microparticle debris population that struck the earth end of LDEF, but not the space end, was also detected and could possibly be the result of a single breakup event at low altitude. These results point to the importance of including discrete orbital debris component contribution changes in flux models in order to achieve accurate predictions of the microparticle environment that a particular spacecraft will experience in earth orbit. The only reliable, verified empirical measurements of these changes are reported in this paper. Further time-resolved in-situ measurements of these debris populations are needed to accurately assess model predictions and mitigation practices

Acetic Acid Aldol Reactions in the Presence of Trimethylsilyl Trifluoromethanesulfonate

In the presence of TMSOTf and a trialkylamine base, acetic acid undergoes aldol addition to non-enolizable aldehydes under exceptionally mild conditions. Acidic workup yields the β-hydroxy carboxylic acid. The reaction appears to proceed via a three-step, one-pot process, including in situ trimethylsilyl ester formation, bis-silyl ketene acetal formation, and TMSOTf-catalyzed Mukaiyama aldol addition. Independently synthesized TMSOAc also undergoes aldol additions under similar conditions

Simultaneous Water Vapor and Dry Air Optical Path Length Measurements and Compensation with the Large Binocular Telescope Interferometer

The Large Binocular Telescope Interferometer uses a near-infrared camera to measure the optical path length variations between the two AO-corrected apertures and provide high-angular resolution observations for all its science channels (1.5-13 $\mu$m). There is however a wavelength dependent component to the atmospheric turbulence, which can introduce optical path length errors when observing at a wavelength different from that of the fringe sensing camera. Water vapor in particular is highly dispersive and its effect must be taken into account for high-precision infrared interferometric observations as described previously for VLTI/MIDI or the Keck Interferometer Nuller. In this paper, we describe the new sensing approach that has been developed at the LBT to measure and monitor the optical path length fluctuations due to dry air and water vapor separately. After reviewing the current performance of the system for dry air seeing compensation, we present simultaneous H-, K-, and N-band observations that illustrate the feasibility of our feedforward approach to stabilize the path length fluctuations seen by the LBTI nuller.Comment: SPIE conference proceeding

Co-phasing the Large Binocular Telescope: status and performance of LBTI/PHASECam

The Large Binocular Telescope Interferometer is a NASA-funded nulling and imaging instrument designed to coherently combine the two 8.4-m primary mirrors of the LBT for high-sensitivity, high-contrast, and high-resolution infrared imaging (1.5-13 um). PHASECam is LBTI's near-infrared camera used to measure tip-tilt and phase variations between the two AO-corrected apertures and provide high-angular resolution observations. We report on the status of the system and describe its on-sky performance measured during the first semester of 2014. With a spatial resolution equivalent to that of a 22.8-meter telescope and the light-gathering power of single 11.8-meter mirror, the co-phased LBT can be considered to be a forerunner of the next-generation extremely large telescopes (ELT).Comment: 8 pages, 5 figures, SPIE Conference proceeding

Buttressing staples with cholecyst-derived extracellular matrix (CEM) reinforces staple lines in an ex vivo peristaltic inflation model

This is the author's accepted manuscript. The final published article is available from the link below. Copyright @ Springer Science + Business Media, LLC 2008Background - Staple line leakage and bleeding are the most common problems associated with the use of surgical staplers for gastrointestinal resection and anastomotic procedures. These complications can be reduced by reinforcing the staple lines with buttressing materials. The current study reports the potential use of cholecyst-derived extracellular matrix (CEM) in non-crosslinked (NCEM) and crosslinked (XCEM) forms, and compares their mechanical performance with clinically available buttress materials [small intestinal submucosa (SIS) and bovine pericardium (BP)] in an ex vivo small intestine model. Methods - Three crosslinked CEM variants (XCEM0005, XCEM001, and XCEM0033) with different degree of crosslinking were produced. An ex vivo peristaltic inflation model was established. Porcine small intestine segments were stapled on one end, using buttressed or non-buttressed surgical staplers. The opened, non-stapled ends were connected to a peristaltic pump and pressure transducer and sealed. The staple lines were then exposed to increased intraluminal pressure in a peristaltic manner. Both the leak and burst pressures of the test specimens were recorded. Results - The leak pressures observed for non-crosslinked NCEM (137.8 ± 22.3 mmHg), crosslinked XCEM0005 (109.1 ± 14.1 mmHg), XCEM001 (150.1 ± 16.0 mmHg), XCEM0033 (98.8 ± 10.5 mmHg) reinforced staple lines were significantly higher when compared to non-buttressed control (28.3 ± 10.8 mmHg) and SIS (one and four layers) (62.6 ± 11.8 and 57.6 ± 12.3 mmHg, respectively) buttressed staple lines. NCEM and XCEM were comparable to that observed for BP buttressed staple lines (138.8 ± 3.6 mmHg). Only specimens with reinforced staple lines were able to achieve high intraluminal pressures (ruptured at the intestinal mesentery), indicating that buttress reinforcements were able to withstand pressure higher than that of natural tissue (physiological failure). Conclusions - These findings suggest that the use of CEM and XCEM as buttressing materials is associated with reinforced staple lines and increased leak pressures when compared to non-buttressed staple lines. CEM and XCEM were found to perform comparably with clinically available buttress materials in this ex vivo model.Enterprise Irelan

One-Pot Enol Silane Formation-Mukaiyama Aldol Reactions: Crossed Aldehyde-Aldehyde Coupling, Thioester Substrates, and Reactions in Ester Solvents

Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote both in situ enol silane/silyl ketene acetal formation and Mukaiyama aldol addition reactions between a variety of reaction partners in a single reaction flask. Isolation of the required enol silane or silyl ketene acetal is not necessary. For example, crossed aldol reactions between α-disubstituted aldehydes and non-enolizable aldehydes yield b- hydroxy aldehydes in good yield. In a related reaction, the common laboratory solvent ethyl acetate functions as both an enolate precursor and a green reaction solvent. When thioesters are employed as enolate precursors, high yields for additions to non-enolizable aldehydes are routinely observed