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61.
Quaternary pyridinium salts were investigated by field desorption, field ionization and electron impact mass spectrometry. Thermal decomposition of the salts under field desorption conditions was found to give very abundant volatile products, identified as the dihydro analogues and the ‘methides’ of the cations. The formation of the volatile compounds, especially those with molecular weights corresponding to those of the (cation ?1), (cation +1) and (cation +13) was studied in detail by deuterium and 13C labelling experiments. 相似文献
62.
Kessel L Kalinin S Nagaraj RH Larsen M Johansson LB 《Photochemistry and photobiology》2002,76(5):549-554
The intrinsic fluorescence from the human lens on excitation in the UV region, referred to as blue lens autofluorescence, increases with age or in the presence of diabetes. The present study reveals that the relative contribution of compounds responsible for the blue autofluorescence appears to be a constant with age. Three potential candidates for the blue fluorescence were also studied with respect to fluorescence spectroscopic properties. These were argpyrimidine and pentosidine, both advanced glycation end products, and 3-hydroxykynurenine (3-OH-kynurenine), a photooxidative derivative of tryptophan. It was shown that the spectral properties of argpyrimidine and pentosidine are compatible with the observed blue fluorescence of the human lens, whereas the fluorescence from 3-OH-kynurenine is negligible. 相似文献
63.
Aaron Goldman Frank J. Murcray Frank H. Murcray David G. Murcray Curtis P. Rinsland 《Mikrochimica acta》1988,95(1-6):409-415
Simultaneous total column amounts of a number of minor and trace atmospheric gases above the South Pole in December 1980 and December 1986 have been deduced from analysis of high resolution solar absorption spectra recorded (by F. J. M. and F. H. M.) from Amundsen-Scott South Pole Station. These spectra also contain some limited information on the vertical profiles of the observed atmospheric gases.The data sets were recorded with a Bomem Michelson-type interferometer and analyzed with a spectral least-squares fitting procedure, utilizing the best available spectroscopic line parameters and absorption cross sections. Because the same instrument, line parameters, and analysis method have been used in analyzing the December 1980 and December 1986 data sets, the precision in comparing the column amounts from these two dates is rather high, about 10–20% for the stronger absorbing gases. For this reason, it has been possible to quantify or determine upper limits for differences between the December 1980 and December 1986 total column amounts, of a number of atmospheric gases including O3, N2O, HNO3, CO2, CH4, and CF2C1
2 (CFC 12). In addition, vertical column amounts for a number of atmospheric gases covered only in the December 1986 observations have been derived, including HC1, NO, NO2, and C2H6. Some of these results will be discussed here. The HC1 measurements are especially interesting since the observed amounts are higher than expected from observations made at lower latitudes in the northern and southern hemispheres. 相似文献
64.
Overgaard J Iversen BB Palii SP Timco GA Gerbeleu NV Larsen FK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(12):2775-2786
The structure and detailed electron density distribution (EDD) of the large octanuclear chromium-wheel host complex [Cr8F8(tBuCO2)16] (1) has been determined from synchrotron X-ray structure factors collected at 16(5) K. The complex has a central cavity with a minimum entry distance between carbon atoms of the pivalate methyl groups (pivalic acid = tBuCO2H) of 4.027(4) A on one side of the molecule and 7.273(4) A on the other. The screened side of the molecule can be "opened" by rotation of methyl groups to create a strained host structure, which is compensated for by improved host-guest and host-solvent interaction. The EDD of the 272-atom complex (1144 e-) was determined by multipole modeling based on the experimental structure factors. 3d orbital populations on the Cr atoms and topological analysis of the EDD show that the covalent part of the metal-ligand interactions consists mainly of sigma donation from the ligands, but that overall the interactions are predominantly electrostatic. The electrostatic potential (EP) has been calculated from the experimental EDD. Knowledge of the geometry of the naked complex 1 as well as the EP in the central cavity of this molecule allows us to deduce which characteristic properties guest molecules must have to be accepted into the void. To probe these predictions, a series of complexes of 1 with different guest inclusions were synthesized (2 = 1 + N,N'-dimethylformamide (DMF), 3 = 1 + N,N'-dimethylacetamide (DMA), 4 = 1 + DMA + DMF, 5 = 1 + 2CH3CN), and their structures were examined by using X-ray diffraction data measured at 120(1) K. Results of these studies indicate that in the crystalline state, the optimal guest molecule should be linear and possess a permanent dipole. Attempts to crystallize the host complex with cations incorporated into the cavity were fruitless, although electrospray ionization mass spectrometry showed that a [1 + potassium]+ entity pre-exists in solution and can be transferred intact into the gas phase. 相似文献
65.
An analytical method based on the use of UV irradiation to produce fluorescent derivatives from four non-fluorescent sulfonylurea herbicides, including chlorsulfuron, metsulfuron methyl, 3-rimsulfuron and sulfometuron methyl is described. Their photochemically-induced fluorescence (PIF) properties in several solvents (water, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile, methanol, ethanol, propan-2-ol and their binary mixtures with water) and micellar solutions of sodium dodecyl sulfate (SDS), and cetyltrimethylammonium chloride (CTAC) are reported. Physicochemical variable influencing the sensitivity of the method have been optimized. A PIF method is developed for the determination of the four herbicides under study. Micellar media are found to provide the best analytical figures of merits. Linear dynamic ranges are established over about two orders of magnitude. The limit of detection (LOD) range from 0.2 to 6 ng ml(-1) according to the compound, with relative standard deviation (RSD) between 1.2 and 3.9%. Examples of applications to the analysis of these herbicides in spiked river water samples are given. The mean recoveries range from 80 to 104%. 相似文献
66.
Using our technique of combustion of small amount of a substance, we determined by calorimetry the standard molar enthalpy of formation in the condensed state and atT=298.15 K of the three isomers of bromo and iodobenzoic acids. Associating to these values their standard molar enthalpies of sublimation previously measured, it was possible to determine their standard molar enthalpies of formation in the gaseous state and atT=298.15 K. The experimental values of the thermodynamic properties f
H
m
o
(cr, 298.15 K), f
H
m
o
(cr, 298.15 K), sub
H
m
o
(298.15 K), and f
H
m
o
(g, 298.15 K) are given for the two series. From the experimental value of the standard molar enthalpy of atomization, it was possible to determine an enthalpy value for the Cb-Br and Cb-I bonds. The experimental and theoretical values of the resonance energy of bromo and iodobenzoic acids are compatible. The relative stability of some monosubstituted derivatives of benzoic acid studied in our laboratory is also discussed.Part I is concerned with Ref. 22 (for bromobenzoic acids) and with Ref. 23 (for iodobenzoic acids). 相似文献
67.
68.
A gas chromatograph/quadrupole mass spectrometer (GC/MS) system was used to supervise a test programme for evaluating the potential of a natural gas storage plant. The dispersion characteristics of a large nitrogen reservoir located in a tight sandstone formation 1600 m below sea level between claystones, was investigated by injection and withdrawal of 350 000 m3 nitrogen with argon as tracer gas. The GC/MS system was installed in a shed in an open field and operated under computer control continuously 24 h a day for three weeks; about 3000 analyses were done. The on-line results were in good agreement with those obtained from additional gas samples withdrawn every 4 h for independent quantitative gas analyses with a purpose-built mass spectrometer. 相似文献
69.
Methods are described for the selective bromine-lithium exchange reaction of bromine-substituted calix[4]arenes with either n-BuLi or t-BuLi in THF. Quenching of the lithiated calix[4]arenes with MeOH, D(2)O, CH(3)SSCH(3), B(OCH(3))(3), DMF, or CO(2) as electrophiles resulted in 5-monosubstituted, 5,17-disubstituted, or 5,11,17,23-tetrasubstituted calix[4]arenes with H, D, SCH(3), B(OH)(2), CHO, or COOH functionalities. 相似文献
70.
Lukas AS Bushard PJ Weiss EA Wasielewski MR 《Journal of the American Chemical Society》2003,125(13):3921-3930
The spin-spin exchange interaction, 2J, in a radical ion pair produced by a photoinduced electron transfer reaction can provide a direct measure of the electronic coupling matrix element, V, for the subsequent charge recombination reaction. We have developed a series of dyad and triad donor-acceptor molecules in which 2J is measured directly as a function of incremental changes in their structures. In the dyads the chromophoric electron donors 4-(N-pyrrolidinyl)- and 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, 5ANI and 6ANI, respectively, and a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor are linked to the meta positions of a phenyl spacer to yield 5ANI-Ph-NI and 6ANI-Ph-NI. In the triads the same structure is used, except that the piperidine in 6ANI is replaced by a piperazine in which a para-X-phenyl, where X = H, F, Cl, MeO, and Me(2)N, is attached to the N' nitrogen to form a para-X-aniline (XAn) donor to give XAn-6ANI-Ph-NI. Photoexcitation yields the respective 5ANI(+)-Ph-NI(-), 6ANI(+)-Ph-NI(-), and XAn(+)-6ANI-Ph-NI(-) singlet radical ion pair states, which undergo subsequent radical pair intersystem crossing followed by charge recombination to yield (3)NI. The radical ion pair distances within the dyads are about 11-12 A, whereas those in the triads are about approximately 16-19 A. The degree of delocalization of charge (and spin) density onto the aniline, and therefore the average distance between the radical ion pairs, is modulated by the para substituent. The (3)NI yields monitored spectroscopically exhibit resonances as a function of magnetic field, which directly yield 2J for the radical ion pairs. A plot of ln 2J versus r(DA), the distance between the centroids of the spin distributions of the two radicals that comprise the pair, yields a slope of -0.5 +/- 0.1. Since both 2J and k(CR), the rate of radical ion pair recombination, are directly proportional to V(2), the observed distance dependence of 2J shows directly that the recombination rates in these molecules obey an exponential distance dependence with beta = 0.5 +/- 0.1 A(-)(1). This technique is very sensitive to small changes in the electronic interaction between the two radicals and can be used to probe subtle structural differences between radical ion pairs produced from photoinduced electron transfer reactions. 相似文献