Sterically controlled syntheses of optically active organic compounds. XV - Syntheses of optically active aspartic acid through beta-lactam.
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The application of an analytical approach combining gas chromatography with mass spectrometry (GC-MS) has shown that the amino acid composition of meteorite extracts is quite complex. A computer was used in the evaluation of the data obtained in the investigations. The computer programs developed have been concerned solely with the mass spectra of amino acids. Specialized programs have been written to determine the number of carbon atoms in an amino acid which is a member of any of three subclasses.
The relativistic effects of the orbiting electrons on a model compound were calculated. The computational method used was based on 'Modified Neglect of Differential Overlap' (MNDO). The compound tetracyanoplatinate was used since empirical measurement and calculations along "classical" lines had yielded many known properties. The purpose was to show that for large molecules relativity effects could not be ignored and that these effects could be calculated and yield data in closer agreement to empirical measurements. Both the energy band structure and molecular orbitals are depicted.
The chemical similarities between comets, carbonaceous chondrites, and interstellar molecules and grains are reviewed first. The evolution of frosty interstellar grains is then followed during the collapse of a molecular cloud fragment and the subsequent formation of the Solar System. The paradigm clarifies the probable origin of the two populations of comets of different symmetry (the Oort Cloud and the Kuiper Belt) and implies an exogenous origin for all carbon and water on earth. This origin is explained by the orbital diffusion of planetesimals that is required by the growth of protoplanets.
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The potential of the high-resolution Electrospray Ionization/Ion Mobility Spectrometry (ESI/IMS) technique as analytical separation tool in analyzing bio-molecular mixtures in the search for the chemical signatures of life is demonstrated. Additional information is contained in the original extended abstract.
For this study, we intend to use a long time series of coarse resolution (8 km and quarter degree) vegetation leaf area index (LAI) and fraction of absorbed PAR (FAPAR) derived from AVHRR data for the time period July 1981 through Dec 2001. The Global Inventory Monitoring and Modeling Studies (GIMMS) data set of AVHRR channel reflectances currently was developed by Dr. Tucker at NASA Goddard. The spatial resolution of the data is 8 km, and a 15-day maximum Normalized Difference Vegetation Index (NDVI) composite time series for the period July 1981 through December 1999 has been produced. The data processing included improved navigation, calibration for intra- and inter-sensor variations, partial atmospheric correction for gaseous absorption and scattering. Stratospheric aerosol effects associated with volcanic eruptions were corrected using a combination of the methods for the data from the period April 1982 - December 1984 (El Chichon) and June 1991 - December 1993 (Mt. Pinatubo).
A system and methodology were developed for the nondestructive qualitative and quantitative analysis of volatile emissions from hydroponically grown 'Waldmann's Green' leaf lettuce (Lactuca sativa L.). Photosynthetic photon flux (PPF), photoperiod, and temperature were automatically controlled and monitored in a growth chamber modified for the collection of plant volatiles. The lipoxygenase pathway products (Z)-3-hexenal, (Z)-3-hexenol, and (Z)-3-hexenyl acetate were emitted by lettuce plants after the transition from the light period to the dark period. The volatile collection system developed in this study enabled measurements of volatiles emitted by intact plants, from planting to harvest, under controlled environmental conditions.
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The use of infrared spectra to determine molecular abundances of icy astronomical objects and to study their chemistry requires laboratory measurements of reference spectra and related quantities, such as the index of refraction (n) and density (p) of candidate ices. Here we present new n and p measurements on ices involving over 30 C-, H-, and O-containing compounds, both acyclic and cyclic, representing seven chemical families. We examine the results in a way that is rare in the astrochemical literature, namely one in which data from an ice formed from molecules of a particular chemical family are compared to measurements on another member of the same family, such as of a homologous series or a pair of isomers. Apart from the intrinsic usefulness of the n and data, a structure-based comparison can help establish trends and identify possibly spurious results. As liquid-phase data sometimes are used in low-temperature astrochemical work in the absence of solid-phase measurements, we compare our new ice results to those for the corresponding room-temperature liquids. We emphasize the use of our n and p data to compute the molar refraction (RM) for each of our ices, and how the resulting RM values compare to those expected from molecular structures. The use of calculated RM values and measured n values to calculate ice densities, in the absence of direct measurements, is also addressed.
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The potential of an Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass spectrometer as analytical instrument for analyzing material extracted from rock and soil samples will be demonstrated.
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