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31.
Ronald Grigg Marie Dowling Maurice W. Jordan Visuvanathar Sridharan 《Tetrahedron》1987,43(24):5873-5886
Hydrazones of aldehydes and ketones undergo intermolecular cycloaddition to electronegative olefins via azomethine imines, formed by a formal 1,2-prototropic shift, in low to moderate yield on heating in xylene or ethanol. In some instances the reaction is diverted to give products derived (at least formally) from an ene reaction. Similar intramolecular cycloadditions occur with unactivated terminal alkenes and alkynes. 相似文献
32.
Ion-molecule reactions with the trimethylsilyl ion were used to distinguish between cis- and trans-1,2-cyclopentanediol isomers. The ion kinetic energy of [Si(CH3)3]+ was varied from 0 eV to 15 eV (center of mass frame of reference). At low ion kinetic energies (<4 eV), there are significant differences in the relative stabilities and decomposition behavior of the adduct ions [M + Si(CH3)3]+. The cis-1,2-cyclopentanediol isomer favors decomposition of [M + Si(CH3)3]+ to yield the hydrated trimethylsilyl ion [Si(CH3)3OH2]+ at m/z 91. For the trans isomer, the formation of the hydrated trimethylsilyl ion is an endothermic process with a definite threshold ion kinetic energy. 相似文献
33.
34.
Pasquale A. Falcigno Stanley Jasne Maurice King 《Journal of polymer science. Part A, Polymer chemistry》1992,30(7):1433-1441
We have synthesized a novel dianhydride, 2,2′-dichloro-4,4′,5,5′-benzophenone tetracarboxylic dianhydride (DCBTDA). Polyimides were synthesized with DCBTDA or 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) and several relatively rigid meta- and para- substituted mononuclear diamines. The BTDA based systems were insoluble in dipolar, aprotic solvents whereas the DCBTDA based polymers displayed enhanced solubility in these solvents. The thermal stability of these polyimides was excellent as measured by 5% weight loss decomposition. The Tg's of the polymers were all above 290°C. 相似文献
35.
Russell SC Czerwieniec G Lebrilla C Tobias H Fergenson DP Steele P Pitesky M Horn J Srivastava A Frank M Gard EE 《Journal of the American Society for Mass Spectrometry》2004,15(6):900-909
The appearance of informative signals in the mass spectra of laser-ablated bio-aerosol particles depends on the effective ionization probabilities (EIP) of individual components during the laser ionization process. This study investigates how bio-aerosol chemical composition governs the EIP values of specific components and the overall features of the spectra from the bio-aerosol mass spectrometry (BAMS). EIP values were determined for a series of amino acid, dipicolinic acid, and peptide aerosol particles to determine what chemical features aid in ionization. The spectra of individual amino acids and dipicolinic acid, as well as mixtures, were examined for extent of fragmentation and the presence of molecular ion dimers, which are indicative of ionization conditions. Standard mixtures yielded information with respect to the significance of secondary ion plume reactions on observed spectra. A greater understanding of how these parameters affect EIP and spectra characteristics of bio-aerosols will aid in the intelligent selection of viable future biomarkers for the identification of bio-terrorism agents. 相似文献
36.
In an attempt to generate antibodies for the development of an immunoanalysis method for potassium and caesium ions, new 1,3-alternate calix[4]arenes-crown-5 and -6 bearing either carboxylic or hydroxyl functions were synthesized in good yields. Their complexation properties towards potassium and caesium ions were investigated using 1H NMR spectroscopy and the usual properties proved to be preserved in the presence of the anchoring arms. 相似文献
37.
Direct loading of polymer matrices in plastic microchips for rapid DNA analysis: A comparative study
C Hurth J Gu M Aboud MD Estes AR Nordquist B McCord F Zenhausern 《Electrophoresis》2012,33(16):2604-2611
We report the design and performance validation of microfluidic separation technologies for human identification using a disposable plastic device suitable for integration into an automated rapid DNA analysis system. A fabrication process for a 15-cm long hot-embossed plastic microfluidic devices with a smooth semielliptical cross section out of cyclic olefin copolymer is presented. We propose a mixed polymer solution of 95% w/v hydroxyethylcellulose and 5% w/v polyvinylpyrrolidone for a final polymer concentration of 2.5 or 3.0% to be used as coating and sieving matrix for DNA separation. This formulation allows preparing the microchip without pretreatment in a single-loading step and provides high-resolution separation (≈1.2 bp for fragments <200 bp), which is superior to existing commercial matrices under the same conditions. The hot-embossed device performance is characterized and compared to injection-molded devices made out of cyclic olefin copolymer based on their respective injector geometry, channel shape, and surface charges. Each device design is assessed by fluorescence videomicroscopy to evaluate the formation of injection plugs, then by comparing electropherograms for the separation of a DNA size standard relevant to human identification. 相似文献
38.
Gansäuer A Knebel K Kube C van Gastel M Cangönül A Daasbjerg K Hangele T Hülsen M Dolg M Friedrich J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2591-2599
The mechanism of catalytic 4-exo cyclizations without gem-dialkyl substitution was investigated by a comparison of cyclic voltammetry, EPR, and computational studies with previously published synthetic results. The most active catalyst is a super-unsaturated 13-electron titanocene(III) complex that is formed by supramolecular activation through hydrogen bonding. The template catalyst binds radicals via a two-point binding that is mandatory for the success of the 4-exo cyclization. The computational investigations revealed that formation of the observed trans-cyclobutane product is not possible from the most stable substrate radical. Instead, the most stable product is formed with the lowest energy of activation from a disfavored substrate in a Curtin-Hammett related scenario. 相似文献
39.
John Bacsa Maurice Okello Pankaj Singh Vasu Nair 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(3):285-288
The conformation and tautomeric structure of (Z)‐4‐[5‐(2,6‐difluorobenzyl)‐1‐(2‐fluorobenzyl)‐2‐oxo‐1,2‐dihydropyridin‐3‐yl]‐4‐hydroxy‐2‐oxo‐N‐(2‐oxopyrrolidin‐1‐yl)but‐3‐enamide, C27H22F3N3O5, in the solid state has been resolved by single‐crystal X‐ray crystallography. The electron distribution in the molecule was evaluated by refinements with invarioms, aspherical scattering factors by the method of Dittrich et al. [Acta Cryst. (2005), A 61 , 314–320] that are based on the Hansen–Coppens multipole model [Hansen & Coppens (1978). Acta Cryst. A 34 , 909–921]. The β‐diketo portion of the molecule exists in the enol form. The enol –OH hydrogen forms a strong asymmetric hydrogen bond with the carbonyl O atom on the β‐C atom of the chain. Weak intramolecular hydrogen bonds exist between the weakly acidic α‐CH hydrogen of the keto–enol group and the pyridinone carbonyl O atom, and also between the hydrazine N—H group and the carbonyl group in the β‐position from the hydrazine N—H group. The electrostatic properties of the molecule were derived from the molecular charge density. The molecule is in a lengthened conformation and the rings of the two benzyl groups are nearly orthogonal. Results from a high‐field 1H and 13C NMR correlation spectroscopy study confirm that the same tautomer exists in solution as in the solid state. 相似文献
40.
A new C19 hydroxylated enyne 15, as potential A-ring building block of vitamin D analogues, was synthesized in enantiomerically pure form in nine steps from (−)-(S)-limonene. This short synthesis involved ozonolyzis of 1,2-limonene oxide followed by a Criegee rearrangement, epoxide trans diaxial ring opening by lithium acetylide, elimination, epoxidation and syn β-elimination of the resulting homopropargylic oxirane. 相似文献