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951.
Zheng SL Gembicky M Messerschmidt M Dominiak PM Coppens P 《Inorganic chemistry》2006,45(23):9281-9289
By selection of different charge-balancing anionic frameworks and different host-to-guest ratios, the photosensitizer-dye cation [Cu(dmp)2]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) has been embedded in a series of three-dimensional host structures. It occurs with variable geometry in different states of aggregation, including weakly interacting monomers, isolated dimers, columns, and layers. A large variation in its emission lifetime is correlated with the relative energy level spacings of the guest- and host-framework components. In a fully saturated host framework, the lifetime exceeds values reported for a series of conventional Cu(dmp)2 salts. 相似文献
952.
A palladium-pivalic acid cocatalyst system has been developed that exhibits unprecedented reactivity in direct arylation. This reactivity is illustrated with the first examples of high yielding direct metalation-arylation reactions of a completely unactivated arene, benzene. Experimental and computational evidence indicates that the pivalate anion is a key component in the palladation/C-H bond breaking event, that it lowers the energy of C-H bond cleavage and acts as a catalytic proton shuttle from benzene to the stoichiometric carbonate base. Eight examples of substituted aryl bromides are included which undergo direct arylation with benzene in 55-85% yield. 相似文献
953.
Lemercier G Bréfuel N Shova S Wolny JA Dahan F Verelst M Paulsen H Trautwein AX Tuchagues JP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(28):7421-7432
The synthesis and characterization of [FeII(trim)2]Cl2 (2), [FeII(trim)2]Br2MeOH (3), and [FeII(trim)2]I2MeOH (4), including the X-ray crystal structure determinations of 2 (50 and 293 K) and 4 (293 K), have been performed and their properties have been examined. In agreement with the magnetic susceptibility results, the M?ssbauer data show the presence of high-spin (HS) to low-spin (LS) crossover with a range of T1/2 larger than 300 K (from approximately 20 K for [FeII(trim)2]F2 (1) to approximately 380 K for 4). All complexes in this series include the same [Fe(trim)2]2+ complex cation: the ligand field comprises a constant contribution from the trim ligands and a variable one originating from the out-of-sphere anions, which is transmitted to the metal center by the connecting imidazole rings and hydrogen bonds. The impressive variation in the intrinsic characteristics of the spin-crossover (SCO) phenomenon in this series is then interpreted as an inductive effect of the anions transmitted to the nitrogen donors through the hydrogen bonds. Based on this qualitative analysis, an increased inductive effect of the out-of-sphere anion corresponds to a decreased SCO temperature T1/2, in agreement with the experimental results. Electronic structure calculations with periodic boundary conditions have been performed that show the importance of intermolecular effects in tuning the ligand field, and thus in determining the transition temperature. Starting with the geometries obtained from the X-ray studies, the [FeII(trim)2]X2 complex molecules 1-4 have been investigated both for the single molecules and the crystal lattices with the local density approximation of density functional theory. The bulk geometries of the complex cations deduced from the X-ray studies and those calculated are in fair agreement for both approaches. However, the trend observed for the transition temperatures of 1-4 disagrees with the trend for the spin-state splittings ES (difference EHS-ELS between the energy of the HS and LS isomers) calculated for the isolated molecules, whereas it agrees with the trend for ES calculated with periodic boundary conditions. The latter calculations predict the strongest stabilization of the HS state for the fluoride complex, which actually is essentially HS above T=50 K, while the most pronounced stabilization of the LS state is predicted for 4, in line with the experimental results. 相似文献
954.
Leuthold LA Mandscheff JF Fathi M Giroud C Augsburger M Varesio E Hopfgartner G 《Rapid communications in mass spectrometry : RCM》2006,20(2):103-110
Desorption electrospray ionization mass spectrometry (DESI-MS) was used as a simple and rapid way to analyze drug tablets and powders without sample preparation. Experiments were performed with a home-made DESI source coupled to a triple-quadrupole linear-ion trap (QqQ(LIT)) mass spectrometer. Twenty-one commercial drugs as well as some illicit Ecstasy tablets and powders were analyzed. MS spectra almost exclusively showed the protonated or deprotonated ion of the drug after directing the pneumatically assisted electrospray onto the tablet's surface. With some tablets, inhomogeneity of the surface resulted in different spectra depending on the spot analyzed, thus showing that DESI could be used for imaging. Directly triggered MS/MS spectra were used for confirmatory analysis, with analysis times often below 10 s per tablet. For illicit Ecstasy tablets, DESI-MS, GC/MS and LC/MS analyses provided similar qualitative results for the main analytes. With MS/MS spectra library comparison or exact mass measurements, this technique could become very powerful for the rapid analysis of unknown tablets and shows the great potential of desorption techniques as an alternative to solution-based analysis. 相似文献
955.
Ghesquière B Goethals M Van Damme J Staes A Timmerman E Vandekerckhove J Gevaert K 《Rapid communications in mass spectrometry : RCM》2006,20(19):2885-2893
Nitrated tyrosines are easily converted into their aminotyrosine equivalents by a reduction step. We here show that this conversion can be exploited to readily discern 3-aminotyrosine peptides in a background of non-nitrated peptides. Furthermore, aminotyrosine peptides are more stable in single mass spectrometry (MS) mode rendering peptide mass maps easier to interpret. One significant caveat of both 3-nitrotyrosine and 3-aminotyrosine peptides is their lack of efficient fragmentation upon collision-induced dissociation (CID) which, in the case of the latter peptides, also produces unexpected, deviating isotopic patterns of fragment ions containing the aminotyrosine residue. The net result is that sequence database searching becomes daunting as the correct peptide is frequently missed since insufficient and/or inaccurate peptide fragments are used. We show that a simple acetylation step, blocking all amines (including aminotyrosine), produces peptides that undergo extensive backbone fragmentation by CID and are thus easily identifiable in databases. Our procedure is additionally illustrated by doubling the number of nitration events mapped in tetranitromethane-nitrated bovine serum albumin (BSA) as compared to a direct analysis of the nitrated peptides using the same amount of material. In conclusion, we here illustrate that this two-step process, heme-mediated reduction and acetylation, can be used for more efficient characterization of protein-bound nitrated tyrosines. 相似文献
956.
Filot MS Leuenberger M Pazdur A Boettger T 《Rapid communications in mass spectrometry : RCM》2006,20(22):3337-3344
An improved method for the determination of deuterium-to-hydrogen (D/H) ratios of non-exchangeable hydrogen in cellulose is presented. The method is based on the equilibration reaction of the hydroxyl hydrogen of cellulose and water vapour of known isotopic composition. The equilibrated cellulose is pyrolysed and the total D/H ratio determined by subsequent online isotope ratio mass spectrometry (IRMS). With a mass balance system the D/H ratio of non-exchangeable hydrogen is recalculated after an empirical calibration has been performed, yielding a mean exchangeability of 0.239 and an equilibrium fractionation factor of 1.082 between the hydroxyl hydrogen of cellulose and water hydrogen at 110 degrees C. Equilibration takes 10 min per sample. Results obtained by this online equilibration method agree very well with values obtained by the nitration technique (R2 = 0.941). The uncertainty of the equilibration method is +/-4 per thousand resulting from a single standard deviation of +/-2.8 per thousand for the equilibration determined by standard cellulose and 2.8 per thousand from the variable exchangeability of the hydroxyl hydrogen in cellulose due to crystalline areas. The latter uncertainty may be lowered by minimising the crystallinity of the cellulose. Advantages of this new technique are (i) the considerably reduced sample amount required (as low as 0.2 mg, ideally 0.5 mg compared with 20 mg for the conventional nitration technique); (ii) an approximately 100-fold reduced process time; and (iii) no need for the hazardous chemicals used in the nitration technique. 相似文献
957.
958.
He K Pauli GF Zheng B Wang H Bai N Peng T Roller M Zheng Q 《Journal of chromatography. A》2006,1112(1-2):241-254
Black cohosh has become one of the most important herbal products in the US dietary supplements market. It is manufactured from roots and rhizomes of Cimicifuga racemosa (Ranunculaceae). Botanical identification of the raw starting material is a key step in the quality control of black cohosh preparations. The present report summarizes a fingerprinting approach based on high performance liquid chromatography-photodiode array/mass spectrometric/evaporative light scattering detection (HPLC-PDA/MS/ELSD) that has been developed and validated using a total of 10 Cimicifuga species. These include three North American species, Cimicifuga racemosa, Cimicifuga americana, Cimicifuga rubifolia, and seven Asian species, Cimicifuga acerina, Cimicifuga biternat, Cimicifuga dahurica, Cimicifuga heracleifolia, Cimicifuga japonica, Cimicifuga foetida, and Cimicifuga simplex. The chemotaxonomic distinctiveness of the HPLC fingerprints allows identification of all 10 Cimicifuga species. The triterpene glycoside cimigenol-3-O-arabinoside (3), cimifugin (12), and cimifugin-3-O-glucoside (18) were determined to be suitable species-specific markers for the distinction of C. racemosa from the other Cimicifuga species. In addition to identification, the fingerprint method provided insight into chemical interconversion processes occurring between the diverse triterpene glycosides contained in black cohosh. The reported method has proven its usefulness in the botanical standardization and quality control of black cohosh products. 相似文献
959.
960.
Montalti M Dolci LS Prodi L Zaccheroni N Stuart MC van Bommel KJ Friggeri A 《Langmuir : the ACS journal of surfaces and colloids》2006,22(5):2299-2303
The fluorescent properties of a new 1,3,5-cyclohexyltricarboxamide-based low-molecular-weight hydrogelator (1) derivatized with one hydrophobic fluorophore and two hydrophilic substituents have been investigated. Gels of 1 are composed of long, nonbranched fibers of uniform diameter, as shown by cryo-transmission electron microscopy (cryo-TEM). The aggregation of the naphthalene fluorophore moieties of the gelator molecules in the gel fibers favors the occurrence of a fast energy migration process that allows a very efficient sensitization of the fluorescence of a hosted fluorophore. Such processes have been investigated by the addition of propyldansylamide (PDNS), at two different concentrations, to gels of 1. Around 30% of the total PDNS added to the gels was found to be incorporated in the gel fibers, as confirmed by deconvolution of the fluorescence spectrum, excited-state lifetime measurements, and steady-state and time-resolved fluorescence anisotropy measurements. Moreover, anisotropy measurements show that the fluorophore that is incorporated within the gel fibers is almost completely immobilized, indicating that the interactions of PDNS with the gelator moieties are very strong. This particular configuration of donor (1) and acceptor (PDNS) molecules leads to a very efficient antenna effect, where 50% of the absorbed photons are funneled through to the dansyl derivative when one PDNS molecule is incorporated in the gel fibers for every 100 gelator molecules. A 5-fold higher concentration of PDNS increases the percentage of funneled photons to 75%. 相似文献