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Regioselective reactions of 3,4-pyridynes enabled by the aryne distortion model.
The pyridine heterocycle continues to play a vital role in the development of human medicines. More than 100 currently marketed drugs contain this privileged unit, which remains highly sought after synthetically. We report an efficient means to access di- and trisubstituted pyridines in an efficient and highly controlled manner using transient 3,4-pyridyne intermediates. Previous efforts to employ 3,4-pyridynes for the construction of substituted pyridines were hampered by a lack of regiocontrol or the inability to later manipulate an adjacent directing group. The strategy relies on the use of proximal halide or sulfamate substituents to perturb pyridyne distortion, which in turn governs regioselectivities in nucleophilic addition and cycloaddition reactions. After trapping of the pyridynes generated in situ, the neighbouring directing groups may be removed or exploited using versatile metal-catalysed cross-coupling reactions. This methodology now renders 3,4-pyridynes as useful synthetic building blocks for the creation of highly decorated derivatives of the medicinally privileged pyridine heterocycle
The mechanical design of a vapor compressor for a heat pump to be used in space
A heat pump developed for use in Spacelab as a stand-alone refrigeration unit as well as within a fluid loop system is discussed. It will provide an active thermal control for payloads. Specifications for the heat pump were established: (1) heat removal rates at the source; (2) heat source temperatures from room temperature; (3) heat-sink fluid temperatures at condenser inlet; and (4) minimum power consumption. A reversed Carnot cycle heat pump using Freon 12 as working fluid incorporating a one-cylinder reciprocating compressor was selected. The maximum crankshaft speed was fixed relatively high at 100 rpm. The specified cooling rates then made it necessary to select a cylinder volume of 10 cu cm, which was obtained with a bore of 40 mm and a stroke of 8 mm
Approach to a rational rotation number in a piecewise isometric system
We study a parametric family of piecewise rotations of the torus, in the
limit in which the rotation number approaches the rational value 1/4. There is
a region of positive measure where the discontinuity set becomes dense in the
limit; we prove that in this region the area occupied by stable periodic orbits
remains positive. The main device is the construction of an induced map on a
domain with vanishing measure; this map is the product of two involutions, and
each involution preserves all its atoms. Dynamically, the composition of these
involutions represents linking together two sector maps; this dynamical system
features an orderly array of stable periodic orbits having a smooth parameter
dependence, plus irregular contributions which become negligible in the limit.Comment: LaTeX, 57 pages with 13 figure
Solidifying system of democracy in the Central and Eastern European new EU members
The paper examines the requirements of an effective and legitimized democratic political system in the process of transition. The analysis and the conclusions are based on the Hungarian experience, which can carefully be applied to all Central and Eastern European (CEE) countries. Special focus is given to the relationship of legal certainty and the efficiency of the democratic system, to the tension between legalism and managerialism and to the characteristics of civil society organizations. In the conclusion special features of the transitional countries are pointed out
Biophysical, morphological, canopy optical property, and productivity data from the Superior National Forest
Described here are the results of a NASA field experiment conducted in the Superior National Forest near Ely, Minnesota, during the summers of 1983 and 1984. The purpose of the experiment was to examine the use of remote sensing to provide measurements of biophysical parameters in the boreal forests. Leaf area index, biomass, net primary productivity, canopy coverage, overstory and understory species composition data are reported for about 60 sites, representing a range of stand density and age for aspen and spruce. Leaf, needle, and bark high-resolution spectral reflectance and transmittance data are reported for the major boreal forest species. Canopy bidirectional reflectance measurements are provided from a helicopter-mounted Barnes Multiband Modular Radiometer (MMR) and the Thematic Mapper Simulator (TMS) on the NASA C-130 aircraft
Ten year change in forest succession and composition measured by remote sensing
Vegetation dynamics and changes in ecological patterns were measured by remote sensing over a 10 year period (1973 to 1983) for 148,406 landscape elements, covering more than 500 sq km in a protected forested wilderness. Quantitative measurements were made possible by methods to detect ecologically meaningful landscape units; these allowed measurement of ecological transition frequencies and calculation of expected recurrence times. Measured ecological transition frequencies reveal boreal forest wilderness as spatially heterogeneous and highly dynamic, with one-sixth of the area in clearings and early successional stages, consistent with recent postulates about the spatial and temporal patterns of natural ecosystems. Differences between managed forest areas and a protected wilderness allow assessment of different management regimes
Precise calibration of LIGO test mass actuators using photon radiation pressure
Precise calibration of kilometer-scale interferometric gravitational wave
detectors is crucial for source localization and waveform reconstruction. A
technique that uses the radiation pressure of a power-modulated auxiliary laser
to induce calibrated displacements of one of the ~10 kg arm cavity mirrors, a
so-called photon calibrator, has been demonstrated previously and has recently
been implemented on the LIGO detectors. In this article, we discuss the
inherent precision and accuracy of the LIGO photon calibrators and several
improvements that have been developed to reduce the estimated voice coil
actuator calibration uncertainties to less than 2 percent (1-sigma). These
improvements include accounting for rotation-induced apparent length variations
caused by interferometer and photon calibrator beam centering offsets, absolute
laser power measurement using temperature-controlled InGaAs photodetectors
mounted on integrating spheres and calibrated by NIST, minimizing errors
induced by localized elastic deformation of the mirror surface by using a
two-beam configuration with the photon calibrator beams symmetrically displaced
about the center of the optic, and simultaneously actuating the test mass with
voice coil actuators and the photon calibrator to minimize fluctuations caused
by the changing interferometer response. The photon calibrator is able to
operate in the most sensitive interferometer configuration, and is expected to
become a primary calibration method for future gravitational wave searches.Comment: 13 pages, 6 figures, accepted by Classical and Quantum Gravit
Precise calibration of LIGO test mass actuators using photon radiation pressure
Precise calibration of kilometer-scale interferometric gravitational wave
detectors is crucial for source localization and waveform reconstruction. A
technique that uses the radiation pressure of a power-modulated auxiliary laser
to induce calibrated displacements of one of the ~10 kg arm cavity mirrors, a
so-called photon calibrator, has been demonstrated previously and has recently
been implemented on the LIGO detectors. In this article, we discuss the
inherent precision and accuracy of the LIGO photon calibrators and several
improvements that have been developed to reduce the estimated voice coil
actuator calibration uncertainties to less than 2 percent (1-sigma). These
improvements include accounting for rotation-induced apparent length variations
caused by interferometer and photon calibrator beam centering offsets, absolute
laser power measurement using temperature-controlled InGaAs photodetectors
mounted on integrating spheres and calibrated by NIST, minimizing errors
induced by localized elastic deformation of the mirror surface by using a
two-beam configuration with the photon calibrator beams symmetrically displaced
about the center of the optic, and simultaneously actuating the test mass with
voice coil actuators and the photon calibrator to minimize fluctuations caused
by the changing interferometer response. The photon calibrator is able to
operate in the most sensitive interferometer configuration, and is expected to
become a primary calibration method for future gravitational wave searches.Comment: 13 pages, 6 figures, accepted by Classical and Quantum Gravit
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