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71.
A custom-built multi-technique portable spectrometer was used to study the vibrational (and electronic) excitations associated with the “anomalous” CO adsorption recently observed on clean and oxidized Cu(100) surfaces at room temperature. Results from the electron energy loss (and thermal desorption) experiments have provided strong evidence for in-situ CO production induced by low-energy electron or ion irradiation of CO or C2H4 on Cu(100). In particular, the C-O vibrational stretch frequency for the room-temperature CO adsorption was found to be red-shifted by 9 meV from its nominal position (259 meV) and could be observed even at temperature as high as 420 K. Several plausible mechanisms involving coadsorbate interactions with CO on metal surfaces have been discussed. A direct interaction model involving partial bonding between CO, adsorbed on an atop site, and a coadsorbed O atom in a four-fold hollow site was found to be adequate in explaining the observed red shift and the apparent stabilization of CO on Cu(100) at room temperature. 相似文献
72.
[formula: see text] A highly diastereoselective, microwave-induced Claisen rearrangement of an appropriately substituted propargylic enol ether allows the formation of the sterically congested C8-C14 bond of azadirachtin. When combined with a radical-mediated cyclization of the corresponding allene, this sequence offers rapid entry to the framework of azadirachtin. 相似文献
73.
Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased. 相似文献
74.
An electrospray ionization (ESI) ambient pressure ion-mobility spectrometer (APIMS) interfaced to an orthogonal reflector time-of-flight mass spectrometer (TOFMS) was evaluated for the first time as a detector for the identification of phenylthiohydantoin (PTH)-derivatized amino acids, the final products in the Edman sequencing process of peptides and proteins. The drift and flight times of the twenty common PTH amino acids were characterized by a well-defined 2-D mobility/mass spectral pattern. The combination of mobility/mass modes of analysis gave rise to a unique trend-line formation for the series of PTH amino acids. In addition, each PTH amino acid had a unique reduced mobility constant K(o), thus enabling the differentiation of all the amino acid derivatives including the PTH-leucine and PTH-isoleucine isomers. More importantly it was shown that it was possible to resolve a complete reference mixture of PTH amino acids in a single experimental run in less than 1 min. Detection limits for the PTH amino acids were found to range from 1.04 to 3.52 ng; indicating that the limits of detection were less than 17.0 pmol for all of the PTH amino acids. 相似文献
75.
N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices. 相似文献
76.
[reaction: see text] The synthesis of allocyathin B(3) from an advanced intermediate possessing the ring system and relative stereochemistry but lacking the isopropyl and hydroxymethyl groups is reported. The isopropyl group was introduced by radical cyclization of a methyl propargyl acetal of an alpha-bromo ketone, and the hydroxymethyl group was generated by Pd-catalyzed carbonylation of a vinyl triflate. The route provides functionalized intermediates that could allow access to more complex members of the cyathin family of diterpenes. 相似文献
77.
The coordination compound [Co(C10H7COO)2(H2O)3]2n
· 4nH2O was prepared by the reaction of 1-naphthoic acid and cobalt(II) acetate tetrahydrate in basic solution, and was fully characterized
by X-ray diffraction, element analysis, FTIR, TG-DTA and luminescent spectra. In the crystal the six-coordinated Co(II) centers
are linked into one-dimensional zigzag chains by water molecules, which are further assembled into a two-dimensional network through weak inter-chain C–H···π interactions.
The solid complex exhibits favorable fluorescent properties similar to those of free ligand at room temperature, which can
be assigned to the intraligand electronic transfer. 相似文献
78.
Hulin Li Boyan Zhang Lin Ma Liliu Wu James Q. Chambers 《Transition Metal Chemistry》1995,20(6):552-556
Summary The spectrochemical, electrochemical and electrocatalytic properties of Co[15]aneN4 ([15]aneN4 = 1,4,8,12-tetraazacyclopentadecane) have been investigated. The results show that, in aqueous solution, this compound mainly exists as three species whose axial coordination positions are occupied by water and/or hydroxy ligands; it is marginal whether other substrates such as Cl– and NO
inf3
sup–
interact with the central ion in acid-base solutions. The approximate Pourbaix diagram of CoIII/II[15]ane N4 was determined. There is an electrochemically-induced isomerization between two trans conformational isomers of the Co[15]aneN4 complexes in acid and netural solutions. The Co[15]aneN4 complex has electrocatalytic properties for reduction of nitrate and nitrite only in strong alkaline solution. 相似文献
79.
S. V. Volkov S. V. Kutyakov A. N. Levov E. I. Polyakova Le Tuan An S. A. Soldatova P. B. Terentiev A. T. Soldatenkov 《Chemistry of Heterocyclic Compounds》2007,43(10):1260-1268
It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4-phenylpiperidine is ring-opened in the presence of
arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation
of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles
and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has
been studied.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1486–1495, October, 2007. 相似文献
80.
Attila R. Imre W. Alexander Van Hook Bong Ho Chang Young Chan Bae 《Monatshefte für Chemie / Chemical Monthly》2003,134(12):1529-1539
Summary. Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N
1=5) to pentacontane (N
1=50)) with an oligostyrene (1241amu, N
2=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains. 相似文献