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81.
Jan Becher Klaus Brsndum Poul Hansen Jens Peter Jan Jacobsen 《Journal of heterocyclic chemistry》1988,25(3):795-798
The anions of 1,4-diaryl-3-buten-2-ones 1 reacts with arylisothiocyanates, yielding intermediates 4 which can ring close to 5,6-dihydro-4H-thiopyran-4-ones 5 . Under similar reaction conditions ethyl 3-oxo-4-pentenoates 7 gives the 6-spiropyrans 9 . Methylation of 3 gives the S-methylated open form 6 . 相似文献
82.
A rapid, robust, sensitive and selective time-based flow injection (FI) on-line solvent extraction system interfaced with electrothermal atomic absorption spectrometry (ETAAS) is described for analyzing ultra-trace amounts of Cr(VI). The sample is initially mixed on-line with isobutyl methyl ketone (IBMK). The Cr(VI) is complexed by reaction with ammonium pyrrolidine dithiocarbamate (APDC), and the non-charged Cr(VI)–PDC chelate formed is extracted into IBMK in a knotted reactor made from PTFE tubing. The organic extractant is separated from the aqueous phase by a gravity phase separator with a small conical cavity and delivered into a collector tube, from which 55 μl organic concentrate is subsequently introduced via an air flow into the graphite tube of the ETAAS instrument. The operations of the FI-system and the ETAAS detector are synchronously coupled. A significant advantage of the approach is that matrix constituents, such as high salt contents, effectively are eliminated. The extraction procedure was optimized by a simplex approach. A central composite design was subsequently employed to verify the estimated operational optimum. An 18-fold enhancement in sensitivity of Cr(VI) was achieved after preconcentration for 99 s at a sample flow rate of 5.5 ml min−1, as compared to direct introduction of 55 μl of sample, yielding a detection limit (3σ) of 3.3 ng l−1. The sampling frequency was 24.2 samples h−1. The proposed method was successfully evaluated by analyzing a NIST Cr(VI)-reference material, synthetic seawater and waste waters, and waste water samples from an incineration plant and a desulphurization plant, respectively. 相似文献
83.
Robert M. Smith Ping Yuan David P. Weiner Caryn R. Dutton David E. Hansen 《Applied biochemistry and biotechnology》1994,47(2-3):329-343
We describe here a novel strategy for the isolation of antibodies with sequence-specific protease activity: the synthesis
of dipeptide haptens in which the targeted peptide bond has been replaced by a ring-strained or torsionally strained hydroxyethylene
transition-state analog. Thus, the analogs mimic both a peptide bond in a distorted, reactive conformation and the transition
state for peptide bond hydrolysis. In order to obtain sequence-specific antibody proteases, these analogs have been flanked
with additional amino acid residues in preparation for immunization. In particular, we have synthesized peptides containing
analogs such as 2-cis-amino-3-cis-hydroxycyclobutane carboxylic acid andendo-(3-amino-2-hydroxy)bicyclo[2.2.1]heptane-7-anti-carboxylic acid. We have also prepared a series of peptide derivatives containing
analogs, such as 2-[3-amino-2-oxo-1-azetidinyl]-3-methylbutanoic acid, in which the targeted peptide bond has been incorporated
into a β-lactam ring. Since the “peptide bond” has been left intact, these species mimic only a distorted ground state. At
present, antibodies are being elicited against a number of the above peptide derivatives. 相似文献
84.
S. A. Catlow G. L. Troyer D. R. Hansen R. A. Jones 《Journal of Radioanalytical and Nuclear Chemistry》2005,263(3):599-603
Summary Long-term risk assessment of residual and disposed nuclear fuel reprocessing waste requires good knowledge of component isotopes with long half-lives. For example, the accuracy of the accepted 126Sn half-life of approximately 100,000 years is insufficient for desired risk assessments. From modeling and sampling, 126Sn is known to exist in Hanford nuclear waste. Excess portions of waste characterization samples were used to isolate 126Sn for measurement of its half-life. Isolation was performed with ion-exchange resins. The resulting 126Sn was gamma-assayed with a hyperpure germanium spectrometer for decay photon identification and activity values. An inductively coupled plasma/mass spectrometer was used to measure the atom quantity of the isolated 126Sn. The separation chemistry, observed gamma energies, and calculated half-life are presented. The half-life of 126Sn estimated in this work is (2.33±0.10) . 105 years. 相似文献
85.
Mohy eldinAbdelFattah Samir ElRayes ElSayedAhmed Soliman Anthony Linden Khaled Abou‐Hadeed Hans‐Jürgen Hansen 《Helvetica chimica acta》2005,88(5):1085-1101
3‐(Phenylsulfonyl)benzo[a]heptalene‐2,4‐diols 1 can be desulfonylated with an excess of LiAlH4/MeLi?LiBr in boiling THF in good yields (Scheme 6). When the reaction is run with LiAlH4/MeLi, mainly the 3,3′‐disulfides 6 of the corresponding 2,4‐dihydroxybenzo[a]heptalene‐3‐thiols are formed after workup (Scheme 7). However, the best yields of desulfonylated products are obtained when the 2,4‐dimethoxy‐substituted benzo[a]heptalenes 2 are reduced with an excess of LiAlH4/TiCl4 at ?78→20° in THF (Scheme 10). Attempts to substitute the PhSO2 group of 2 with freshly prepared MeONa in boiling THF led to a highly selective ether cleavage of the 4‐MeO group, rather than to desulfonylation (Scheme 13). 相似文献
86.
Photolysis of 3-Methyl-2, 1-benzisoxazole (3-Methylanthranil) and 2-Azido-acetophenone in the Presence of Sulfuric Acid and Benzene Derivatives Irradiation of 3-methylanthranil ( 1 ) in acetonitrile in the presence of sulfuric acid and benzene, toluene, p-xylene, mesitylene or anisole with a mercury high-pressure lamp through a pyrex filter yields beside varying amounts of 2-amino-acetophenone ( 3 ) and 2-amino-5-hydroxy- ( 4a ) and 2-amino-3-hydroxy-acetophenone ( 4b ) the corresponding diphenylamine derivatives 5 (see Table 1). In the case of toluene and anisole mixtures of the corresponding ortho- and para-substituted isomers ( 5b, 5d or 5g, 5i respectively), but no meta-substituted isomers ( 5c or 5h ) are obtained. In addition to these products, the irradiation of 1 in the presence of anisole yields also 2-amino-5-(4′-methoxyphenyl)-acetophenone ( 7 ), 2-amino-3-(4′-methoxyphenyl)-acetophenone ( 8 ) and 2-methoxy-9-methyl-acridine ( 6 ; see Scheme 1). The latter product is also formed thermally by acid catalysis from the diphenylamine derivative 5i . Irradiation of 2-azido-acetophenone ( 2 ) in acetonitrile solution in the presence of sulfuric acid and benzene leads to the formation of 1, 3, 4a, 4b, 5a and 9 (see Table 2). Compounds 3, 4a, 4b and 5a are also obtained after acid catalyzed decomposition of 2 in the presence of benzene. Thus, it is concluded that irradiation of 1 or 2 in the presence of sulfuric acid yields 2-acetyl-phenylnitrenium ions 10 in the singlet ground state which will undergo electrophilic substitution of the aromatic compounds, perhaps via the π-complex 11 (see Scheme 2). 相似文献
87.
Ursula Schmid Paul Gilgen Heinz Heimgartner Hans-Jürgen Hansen Hans Schmid 《Helvetica chimica acta》1974,57(5):1393-1403
Irradiation of 2, 3-diphenyl-2H-azirine ( 1a ) and 1-azido-1-phenyl-propene, the precursor of 2-methyl-3-phenyl-2H-azirine ( 1b ), in benzene, with a high pressure mercury lamp (pyrex filter) in the presence of acid chlorides yields the oxazoles 5a–d (Scheme 2). Photolysis of 2, 2-dimethyl-3-phenyl-2H-azirine ( 1c ) under the same conditions gives after methanolysis the 5-methoxy-2, 2-dimethyl-4-phenyl-3-oxazolines 7a, b, d , while hydrolysis of the reaction mixture leads to the formation of the 1, 2-diketones 8a, c, d (Scheme 4). The suggested reaction path for all these reactions is a 1, 3-dipolar cycloaddition of the photochemically generated benzonitrilemethylides 2 to the carbonyl double bond of the acid chlorides to give the intermediates 4 , followed by either elimination of hydrogen chloride or solvolysis (Schemes 2 and 4). Irradiation of 1c in the presence of acetic acid anhydride leads via the intermediate 9 to the 5-hydroxy-3-oxazoline 10 and the 5-methylidene-3-oxazoline 11 (Scheme 5). 相似文献
88.
Yao Chang Jiayue Yang Zhichao Chen Zhiguo Zhang Yong Yu Qingming Li Zhigang He Weiqing Zhang Guorong Wu Rebecca A. Ingle Matthew Bain Michael N. R. Ashfold Kaijun Yuan Xueming Yang Christopher S. Hansen 《Chemical science》2020,11(19):5089
Chemical processing in the stratospheres of the gas giants is driven by incident vacuum ultraviolet (VUV) light. Ethane is an important constituent in the atmospheres of the gas giants in our solar system. The present work describes translational spectroscopy studies of the VUV photochemistry of ethane using tuneable radiation in the wavelength range 112 ≤ λ ≤ 126 nm from a free electron laser and event-triggered, fast-framing, multi-mass imaging detection methods. Contributions from at least five primary photofragmentation pathways yielding CH2, CH3 and/or H atom products are demonstrated and interpreted in terms of unimolecular decay following rapid non-adiabatic coupling to the ground state potential energy surface. These data serve to highlight parallels with methane photochemistry and limitations in contemporary models of the photoinduced stratospheric chemistry of the gas giants. The work identifies additional photochemical reactions that require incorporation into next generation extraterrestrial atmospheric chemistry models which should help rationalise hitherto unexplained aspects of the atmospheric ethane/acetylene ratios revealed by the Cassini–Huygens fly-by of Jupiter.The vacuum ultraviolet photodissociation dynamics of ethane provide clues for modelling the atmospheric chemistry of the gas giants. 相似文献
89.
1-cis, 2-cis-Dipropenylbenzene (cis, cis- 1 ) isomerises thermally at 215–235° with 1st order kinetics to give trans, cis- 1 and vice versa. At equilibrium 89% trans, cis- and 11% cis, cis- 1 are present. It is shown by thermal rearrangement of cis, cis-2′, 2″-d2- 1 that the isomerisation is attributable to aromatic [1, 7a]-sigmatropic H-shifts. trans, trans- 1 rearranges thermally at 225–245° to yield 2, 3-dimethyl-1, 2-dihydronaphthalene ( 2 ). The formation of 2 can be visualized by disrotatory ring closure followed by an aromatic [1, 5s]-sigmatropic H-shift. 2 is also formed when, cis, cis- or trans, cis- 1 are heated for 153 h at 225°. Besides 2 a small amount (3%) of 1-ethyl-1, 2-dihydronaphthalene ( 5 ) is formed. The rearrangement of trans, trans- 1 and trans, trans-2′, 2″-d2- 1 shows a secondary isotope effect kH/kD = 0,90. 相似文献
90.
Hansen PH Malmsten M Bergenståhl B Bergström L 《Journal of colloid and interface science》1999,220(2):269-280
Orthokinetic aggregation of colloids trapped at the air–liquid interface was studied by direct imaging in a couette cell. This method allowed us to follow the temporal evolution of both the cluster-mass distribution and the cluster structure at a shear rate where Brownian aggregation is suppressed. The interactions between the monodisperse latex particles floating at the air–liquid interface were controlled either by varying the electrolyte concentration or by creating a bidisperse system through the addition of small particles. The results show that the clusters in all of the systems are characterized by a high fractal dimension, indicating that the clusters are rearranged and densified by the shear. Kinetic analysis suggests that aggregation of monodisperse systems mainly proceeds through homogeneous aggregation, i.e., large clusters sticking to other large clusters. The bidisperse system, finally, with a size ratio around 10, favored a more heterogeneous aggregation among small and large clusters throughout the aggregation process; a slightly lower fractal dimension was observed compared to the strongly aggregated monodisperse system. 相似文献