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81.
Hans. R. Kricheldorf William E. Hull 《Journal of polymer science. Part A, Polymer chemistry》1978,16(3):583-595
The tripeptides Phe-Gly-Gly, β-Ala-Gly-Gly, and ?-Aca-Gly-Gly as well as the peptide derivatives δ-isothiocyanatovaleroyl-Gly-Gly and ?-isothiocyanatocaproyl-Gly-Gly were synthesized by using known methods so that the peptide nitrogen between the two glycyl residues was isotopically enriched in 15N to a level of 0.8–0.9%. These monomer units were then used to produce the sequence polymers (Phe-Gly-Gly)n, (β-Ala-Gly-Gly)n, (δ-Ava-Gly-Gly)n, and (?-Aca-Gly-Gly)n. The 18.24 MHz 15N-NMR spectra of the oligo- and polypeptides were obtained by using trifluoroacetic acid as solvent, since the solutions have relatively low viscosity and exhibit a strong negative nuclear Overhauser enhancement of the 15N signals. For comparison, 15N-NMR spectra of the homopolymers (Gly)n, (β-Ala)n, (γ-Abu)n, (δ-Ava)n, and (?-Aca)n were also recorded. The 15N signals from the ω-aminoacyl residues in the sequence polymers appear up to 11 ppm upfield of the signals observed for the homopolyamides. The 15N signals from the two glycyl residues are separated by 3–7 ppm. Comparison with the 13C-NMR spectra of the same polymers indicates that 15N-NMR is better suited for the characterization and sequence analysis of these types of polymers. 相似文献
82.
Barry SJ Carr RM Lane SJ Leavens WJ Monté S Waterhouse I 《Rapid communications in mass spectrometry : RCM》2003,17(6):603-620
A simple method has been developed for the pre-column derivatisation of low molecular weight primary and secondary amines and carboxylic acids using quaternary nitrogen compounds to enhance their detection by liquid chromatography/electrospray ionisation mass spectrometry (LC/ESI-MS). The synthesis of seven novel quaternary nitrogen reagents is described. The derivatives are designed to be relatively small molecules to avoid some of the steric hindrance problems that may be associated with larger derivatisation reagents. The compounds have amine and carboxylic acid functional groups with which to derivatise carboxylic acids and amines, respectively. Two of the compounds contain a bromine atom in order to assess the advantages of a bromine isotope pattern in the mass spectra. This acts as a simple marker for derivatisation and enables data processing by cluster analysis.Activation of the carboxylic acid group was achieved by the use of either 1-chloro-4-methylpyridinium iodide (CMPI) or the more reactive 1-fluoro-4-methylpyridinium p-toluenesulphonate (FMP).1 Using both of these active reagents, the degree of nucleophilic substitution was investigated for the derivatisation of a variety of small molecules. Whilst giving some increase in the ESI-MS response for the derivatised compounds, the FMP itself acted as a derivatising reagent in a competing reaction. In the light of this finding, FMP was reacted with the test compounds separately and gave positive results as a derivatising reagent. Detection of the 'pre-charged' derivatives of amines and carboxylic acids by LC/ESI-MS was investigated with respect to their ESI response and chromatography. 相似文献
83.
Richard R. Izac Maury M. Bandurraga John M. Wasylyk Fred W. Dunn William Fenical 《Tetrahedron》1982,38(2):301-304
Examinations of the extracts of 8 taxonomically-diverse marine soft-corals (Orders Gorgonaceae, Alcyonaceae and Stolonifera, Subclass Octocorallia, Phylum Cnidaria), have resulted in the isolation of 4 new sesquiterpenoids (1–4) of the germacrene type. Three previously known germacrene derivatives (5–7), and the elemane 8, have also been isolated, and complete 1H and 13C NMR assignments for these compounds are reported. 相似文献
84.
Abstract —Various low-potential viologen dyes enhance light-induced absorption changes in the near-infrared region (ΔA870) in chromatophore preparations from Rhodospirillum rubrum in the presence of dichlorophenol indophenol and a high concentration of ascorbate (DCPIP + asc). An increase in ΔA870 was also observed in large reaction-center preparations from R. rubrum with viologens in the presence of ascorbate. Our results indicate that E'0 , of the primary electron acceptor X may be as low as -0.37 V, as suggested recently by P. A. Loach (1973, personal communication). 相似文献
85.
William T. Simpson 《Theoretical chemistry accounts》1972,23(4):295-308
For a particular model with two electronic states, each with two vibrations, the dipole correlation function governing electronic absorption is e ?iωOt cosγt with spectrum ω 0±γ. The function starts as e ?iωOt (γ?ω 0), with Fourier transform peaking around ω 0 instead of ω 0±γ, and this is associated with vertical excitation. After a time t~2/γ the spectrum goes over into the normal one. As a generalization, a procedure is outlined for characterizing the state reached first after interaction with light is initiated. Finally it is suggested that one can understand aspects of internal conversion by analogy with the case of vertical excitation. 相似文献
86.
Samuel K Yin W Stearns RA Tang YS Chaudhary AG Jewell JP Lanza T Lin LS Hagmann WK Evans DC Kumar S 《Journal of mass spectrometry : JMS》2003,38(2):211-221
Metabolic activation of drug candidates to electrophilic reactive metabolites that can covalently modify cellular macromolecules may result in acute and/or idiosyncratic immune system-mediated toxicities in humans. This presents a significant potential liability for the future development of these compounds as safe therapeutic agents. We present here an example of an approach where sites of metabolic activation within a new drug candidate series were rapidly identified using online liquid chromatography/multi-stage mass spectrometry on an ion trap mass spectrometer. This was accomplished by trapping the reactive intermediates formed upon incubation of compounds with rat and human liver microsomes as their corresponding glutathione conjugates and mass spectral characterization of these thiol adducts. Based on the structures of the GSH adducts identified, potential sites and mechanisms of bioactivation within the chemical structure were proposed. These metabolism studies were interfaced with iterative structural modifications of the chemical series in order to block these bioactivation sites within the molecule. This strategy led to a significant reduction in the propensity of the compounds to undergo metabolic activation as evidenced by reductions in the irreversible binding of radioactivity to liver microsomal material upon incubation of tritium-labeled compounds with this in vitro system. With the efficiency and throughput achievable with such an approach, it appears feasible to identify and address the metabolic activation potential of new drug leads during routine metabolite identification studies in an early drug discovery setting. 相似文献
87.
The copper-catalyzed pyrolysis of 1-diazo-3-(pyrrol-1-yl)-2-propanone (1a) and 1-diazo-4-(pyrrol-1-yl)-2-butanone (1b) in benzene solution gave 1 H-pyrrolizin-2-(3H)-one (4a) and 5,6-dihydroindolizin-7 (8H)-one (4b) , respectively, in quantitative yield. Similar pyrolysis of 1-diazo-4-(3-methylindol-1-yl)-2-butanone (9) was less efficient giving 1-methylbenzo[b]-5,6-dihydroindroindolizin-7 (8H)-one (10) and 4-(3-methylindol-1-yl)-but-l-en-3-one (11) in 7% and 24% yield, respectively. 相似文献
88.
Zhu H Chai J Chandrasekhar V Roesky HW Magull J Vidovic D Schmidt HG Noltemeyer M Power PP Merrill WA 《Journal of the American Chemical Society》2004,126(31):9472-9473
The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3. 相似文献
89.
A systematic optimization strategy for reverse-phase h.p.l.c. is used to produce complete separation of all components of a mixture containing two coumarins, umbelliferone and scopoletin, and the cis-trans isomers of two cinnamic acids, p-coumaric and ferulic. A series of experiments gives retention time data for each of these substances in four citric acid-buffered mobile phases. A mathematical model fitted to this data gives model parameters that provide the basis for a window diagram of relative retentions vs. mobile phase pH. The window diagram gives an estimate of the mobile phase pH required for optimum separation. 相似文献
90.
Marshall M. Siegel Rushung Tsao William Bouley Theodore Kornas Glen Brubaker 《Journal of the American Society for Mass Spectrometry》1993,4(6):504-506
An inexpensive multisample fast-atom bombardment (FAB) probe assembly was designed for high-throughput analysis of samples on a VG ZAB-SE mass spectrometer. The system consists of a vacuum lock system and a FAB probe whose tip contains five or more sample wells. The probe enters the mass spectrometer source region perpendicular to the secondary ion beam axis, The probe is maintained at high voltage on contact with a spring clip attached to the screen plate of the source block. Sample throughput with the multisample probe is twice that of a coaxial probe, with about twice the sensitivity and no sample cross contamination. 相似文献