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101.
Dirk JohrendtGunter Kotzyba Henning TrillBernd D. Mosel Hellmut EckertThomas Fickenscher Rainer Pöttgen† 《Journal of solid state chemistry》2002,164(2):201-209
Single-phase samples of REAgMg (RE=La, Ce, Eu, Yb) and EuAuMg were prepared by reacting the elements in sealed tantalum tubes in a high-frequency furnace. LaAgMg and CeAgMg adopt the hexagonal ZrNiAl-type structure, while EuAgMg, YbAgMg, and EuAuMg crystallize with the orthorhombic TiNiSi type. Chemical bonding was exemplarily investigatedfor EuAgMg and EuAuMg on the basis of TB-LMTO-ASAcalculations. Magnetic susceptibility measurements indicatePauli paramagnetism for LaAgMg and YbAgMg with room-temperature susceptibilities of 2.4(1)×10−9 and 1.5(1)×10−9 m3/mol, respectively. CeAgMg remains paramagnetic down to 2 K. The experimental magnetic moment of 2.52(2) μB/Ce above 50 K is compatible with trivalent cerium. EuAgMg and EuAuMg are paramagnetic above 50 K with experimentalmagnetic moments of 7.99(5) μB/Eu for the silver and 7.80(5) μB/Eu for the gold compound, indicating divalent europium. Ferromagnetic ordering is detected at TC=22.0(3) K (EuAgMg) and TC=36.5(5) K (EuAuMg). At 4.2 K and 5 T the saturation magnetizations are 7.1(1) and 7.3(1) μB/Eu for EuAgMg and EuAuMg, respectively. According to the very small hysteresis, EuAgMg and EuAuMg may be classified as soft ferromagnets. All compounds are metallic conductors. For EuAgMg and EuAuMg freezing of spin-disorder scattering is observed below TC. At 78 K 151Eu Mössbauer spectra show isomer shifts of −9.00(4) and −8.72(8) mm/s for EuAgMg and EuAuMg, respectively. Full magnetic hyperfine field splitting is detected at 4.2 K with hyperfine fields of 17.4(1) and 18.3(2) T at the europium nuclei of EuAgMg and EuAuMg. 相似文献
102.
Guldi DM Zilbermann I Anderson G Kotov NA Tagmatarchis N Prato M 《Journal of the American Chemical Society》2004,126(44):14340-14341
Novel organic (positively charged fullerene)-inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor-acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states. 相似文献
103.
Kumar K Michalik D Garcia Castro I Tillack A Zapf A Arlt M Heinrich T Böttcher H Beller M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):746-757
A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals. 相似文献
104.
Pocha R Johrendt D Ni B Abd-Elmeguid MM 《Journal of the American Chemical Society》2005,127(24):8732-8740
The crystal structures of the tetrahedral cluster compounds GaNb(4)S(8) and GaTa(4)Se(8) were determined by single-crystal X-ray diffraction. They crystallize in the cubic GaMo(4)S(8) structure type (F3m), which can be derived from the spinel type by shifting the metal atoms off the centers of the chalcogen octahedra along [111]. Electrical resistivity and magnetic susceptibility measurements show that the electronic conduction originates from hopping of localized unpaired electrons (S = (1)/(2)) among widely separated Nb(4) or Ta(4) clusters, and thus these materials represent a new class of Mott insulators. Under high pressure we find that GaNb(4)S(8) undergoes a transition from the Mott insulating to a superconducting state with T(C) up to 4 K at 23 GPa, similar to GaNb(4)Se(8) and GaTa(4)Se(8). High-pressure single-crystal X-ray studies of GaTa(4)Se(8) reveal that the superconducting transition is connected with a gradual decrease of the octahedral distortion with increasing pressure. DFT band structure calculations show that weakly coupled cluster orbitals are responsible for a high density of states at the Fermi level. The correct insulating magnetic ground state for GaNb(4)S(8) with mu(eff) = 1.73 mu(B) is for the first time achieved by the LDA+U method using U = 6 eV and rhombohedral symmetry. 相似文献
105.
Bissessur R Haines RI Hutchings DR Brüning R 《Chemical communications (Cambridge, England)》2001,(17):1598-1599
A novel macrocycle-MoS2 nanocomposite has been synthesized and characterized using the exfoliation/restacking properties of LiMoS2, providing the first of a new family of intercalation compounds. 相似文献
106.
F. Chisela D. Gawlik P. Brätter 《Journal of Radioanalytical and Nuclear Chemistry》1987,112(2):293-308
Boron carbide (B4C) and boron nitride (BN) irradiation filters have been constructed and used for epithermal neutron activation analysis of biological materials. The major advantage offered by these filters in this application is the substantial reduction of interfering matrix activities. Consequently some trace elements of interest can be determined instrumentally with minimum delay. The filters are particulary beneficial if utilized in short reactor irradiations for rapid analysis of biological materials. 相似文献
107.
Alexander Chernega Dirk. L. Elend Christian A.P. Smethurst Paul M. Roberts Andrew D. Smith G. Darren Smyth 《Tetrahedron》2007,63(30):7036-7046
A three-step protocol for the asymmetric synthesis of a range of β-substituted Baylis-Hillman products has been developed. This procedure involves the diastereoselective conjugate addition of lithium (R)-N-methyl-N-(α-methylbenzyl)amide to an α,β-unsaturated ester to generate an N-protected β-amino ester in high de. Subsequent asymmetric aldol reaction via deprotonation with LDA, transmetallation with B(OMe)3 and addition of an aldehyde gives a range of syn-aldol products in moderate to high de. Purification of the syn-aldol products to homogeneity followed by tandem N-oxidation and Cope elimination gives the desired β-substituted Baylis-Hillman products in good yield and high de and ee. 相似文献
108.
In the EURACHEM/CITAC draft ”Quantifying uncertainty in analytical measurement” estimations of measurement uncertainty in
analytical results for linear calibration are given. In this work these estimations are compared, i.e. the uncertainty deduced
from repeated observations of the sample vs. the uncertainty deduced from the standard residual deviation of the regression.
As a result of this study it is shown that an uncertainty estimation based on repeated observations can give more realistic
values if the condition of variance homogeneity is not correctly fulfilled in the calibration range. The complete calculation
of measurement uncertainty including assessment of trueness is represented by an example concerning the determination of zinc
in sediment samples using ICP-atomic emission spectrometry.
Received: 9 February 2002 Accepted: 17 April 2002 相似文献
109.
In this study we have compared different ligands containing three or more hetero-atoms (N, O and/or S) with respect to their ability to form tridentate complexes with a Tc-tricarbonyl moiety. Comparison of each ligand in a competition reaction with histidine first and then with each other compound allowed to rank the ligands according to their ability of complex formation with the [99mTc(CO)3]+ precursor from diethylenetriamine (most efficient of the studied ligands) to nitrilotriacetic acid (weakest complexing properties). The results provide insight in the structural requirements for the formation of stable Tc-tricarbonyl complexes and suggest preferred combinations and arrangements of the hetero-atoms involved in the complex formation. They also give a good indication which type of ligand is most appropriate to modify biomolecules for an efficient and stable labelling with a Tc-tricarbonyl moiety. 相似文献
110.
A simple flow-injection system for determination of traces of fluoride by means of the fluoride-selective electrode is presented. A comparison of several flow-cell arrangements confirmed the advantages of a well-jet design. Systematic investigations of the parameters affecting response times (i.e., polishing procedure, flow rate, carrier composition) established the optimal experimental conditions for measurements down to 1 μg l?1 fluoride. Calibration plots in the lower μg l?1 range were neither Nernstein nor linear, but good precision (0.5–5%) was obtained even when the potential differences for concentration steps of one decade were as small as 3 mV. 相似文献