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61.
Blake AJ Bencini A Caltagirone C De Filippo G Dolci LS Garau A Isaia F Lippolis V Mariani P Prodi L Montalti M Zaccheroni N Wilson C 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2771-2779
The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions. 相似文献
62.
Joanna Szpunar-Łobińska Michiel Ceulemans Wilfried Dirkx Claudia Witte Ryszard Łobiński Freddy C. Adams 《Mikrochimica acta》1994,113(3-6):287-298
Interferences in trace and ultratrace speciation analysis of organotin and organolead compounds in various samples by gas chromatography coupled with atomic absorption spectrometry (AAS) and/or microwave induced plasma atomic emission spectrometry (MIP AES) are investigated. Particular attention is given to the effects of matrix co-extractives and reagents impurities introduced during sample preparation. Their influence on the detection limits is discussed in terms of baseline noise level, blank value, formation of artefacts and signal suppression. Loss of column resolution during the analysis of some matrices is observed. 相似文献
63.
Trimethylsilyl Derivatives of Vb Elements. VII. Crystal Structures of Lithium Bis(trimethylsilyl)bismuthide · DME and of Tetrakis(trimethylsilyl)dibismuthane as well as Some Comments on the Crystal Structure of Bis(4-methoxyphenyl)ditellane Colourless lithium bis(trimethylsilyl)bismuthide · DME 1 1,2-Dimethoxyethan (DME); Tetrahydrofuran (THF) 1 and green, metallic lustrous tetrakis(trimethylsilyl)dibismuthane 2 crystallize isotopic to their antimony homologues [1, 2]. As it is shown by crystal structure determinations { 1 : ?90°C; I 4 2d; a = 1017,3(4); c = 3738,0(26) pm; Z = 8; R w = 0,065; 2 : + 20°C; P2 1 /c; a = 680,9(4); b = 1704,8(13); c = 1197,9 (10) pm; β = 119,46(6)°; Z = 2; R w = 0,084} both compounds form chains which in the case of bismuthide 1 are built up as screws of alternating bismuth and lithium atoms; bonding further to two trimethylsilyl groups or to the chelating DME ligand both atoms gain coordination number 4 {Li? Bi 292(3); Bi? Si 263.3(14) pm; Bi? Li? Bi 132(1); Li? Bi? Li 148(1); φ(Li? Bi? Li? Bi) 83°}. In the case of dibismuthane 2 the centrosymmetric molecules are strung, their Bi-Bi groups forming nearly linear zigzag chains with shortened intermolecular contact distances {Bi-Bi 303.5(3); Bi …? Bi 380.4(3); Bi? Si 268 pm; Bi? Bi …? Bi 169; Bi? Bi? Si 97.4(5) and 92.0(5)°}. Structure and properties of 2 are compared with those of similar compounds; the crystal structure of brown, green metallic lustrous bis(4-methoxyphenyl)ditellane 5 already published by Ludlow and McCarthy[3] is reinvestigated with respect to very short intermolecular Te…?Te contacts. 相似文献
64.
Attila Szorcsik Andrea Deák Zoltán A. Fekete Claudia Pellerito 《Journal of organometallic chemistry》2004,689(17):2762-2769
Nine complexes of tBu2Sn(IV)2+ were obtained in the solid state with ligands containing -COOH group(s) and aromatic {N} donor atom. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. It was found that in most cases the -COO− groups are co-ordinated in monodentate manner. Nevertheless, in some of our complexes, the -COO− group forms bridges between two central {Sn} atoms resulting in the formation of an oligomeric structure, a motif that is characteristic only to the nicotinate compound. These pieces of information and the rationalisation of the experimental 119Sn Mössbauer nuclear quadrupole splittings, Δ, - according to the point charge model formalism - support the formation of octahedral (Oh) or trigonal bipyramidal (TBP) molecular structures. The X-ray diffraction analysis of one complex obtained as single crystal revealed the distortion of the TBP geometry towards square pyramidal (SP) one. This was rationalised by PM3 molecular modelling of the tBu2Sn(pdc) complex. In the asymmetric unit, the two chemically similar but symmetry independent molecules form pseudo-dimers, in which the Sn?Sn separation amounts to ca. 6.4 Å. The crystal lattice is stabilised by C-H?O hydrogen bonding between individual molecules. 相似文献
65.
Römer W Lam YH Fischer D Watts A Fischer WB Göring P Wehrspohn RB Gösele U Steinem C 《Journal of the American Chemical Society》2004,126(49):16267-16274
We report for the first time on pore-suspending lipid bilayers, which we call micro-black lipid membranes (micro-BLMs), based on a highly ordered macroporous silicon array. Micro-BLMs were established by first functionalizing the backside porous silicon surface with gold and then chemisorbing 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol followed by spreading 1,2-diphytanoyl-sn-glycero-3-phosphocholine dissolved in n-decane. Impedance spectroscopy revealed the formation of single lipid bilayers confirmed by a mean specific capacitance of 0.6 +/- 0.2 microF/cm2. Membrane resistances were in the G omega-regime and beyond. The potential of the system for single channel recordings was demonstrated by inserting the transmembrane domain of the HIV-1 accessory peptide Vpu(1-32), which forms helix bundles with characteristic opening states. We elucidated different amilorides as potential drugs to inhibit channel activity of Vpu. 相似文献
66.
Wilson Cunico Claudia R. B. Gomes Solange M. S. V. Wardell John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):o411-o414
rac‐2‐Isopropyl‐3‐(2‐nitrobenzyl)‐1,3‐thiadiazolin‐4‐one, C13H16N2O3S, is a rare example of a racemate crystallizing in the space group P212121, with one molecule each of S and R configurations, whose conformations are almost mirror images, within the asymmetric unit. The molecules of S configuration are linked by two C—H...O hydrogen bonds into a three‐dimensional framework, and the molecules of R configuration are linked by two further C—H...O hydrogen bonds into a different type of three‐dimensional framework; the two frameworks are linked by a fifth C—H...O hydrogen bond. 相似文献
67.
Francesco Frusteri Lorenzo Spadaro Claudia Espro Adolfo Parmaliana Francesco Arena 《天然气化学杂志》2002,(Z2)
The liquid-phase partial oxidation of propane in the presence of the Fen+/H2O2 Fenton system at 70℃ and 1.4 atm on silica supported Nafion catalysts has been investigated. The reaction proceeds via a radical reaction path the efficiency of which is improved by silica-supported Nafion catalysts. Because of the direct relationship between reaction rate and concentration of sulphonic acid sites of Nafion catalysts, it is inferred that the active phase enahnces the kinetics of propane conversion by promoting the rate of active radicals generation. 相似文献
68.
Concetta De Stefano Claudia Foti Antonio Gianguzza Frank J. Millero Silvio Sammartano 《Journal of solution chemistry》1999,28(7):959-972
The hydrolysis of trimethyltin(IV) has been studied by potentiometry (H+ -glass electrode) and calorimetry in various salt media (NaNO3, NaCl, KCl, Na2SO4, and NaNO3—NaCl mixtures). The effect of ionic strength on the hydrolysis constants is accounted for by a simple Debye–Hückel type equation and by Pitzer equations. The results allow us to obtain H for hydrolysis and the temperature dependence of the Pitzer parameters. The resulting coefficients can be used to examine the speciation of (CH3)3Sn+ in multicomponent electrolyte solutions, such as natural waters, over a wide range of temperature and ionic strength. 相似文献
69.
70.
Ponce De León CA Montes Bayón M Caruso JA 《Analytical and bioanalytical chemistry》2002,374(2):230-234
Vitamin E supplements are either isolated from plants sources or prepared synthetically. Isolation from plants includes eight different tocopherol structures. Vitamin E synthesis includes seven different stereoisomers, which involves the use of several catalysts that may lead to trace element contamination in the vitamin. The use of ICP-MS is an ideal technique for detecting these trace elements. However, the oily nature of the samples requires the development of a sample preparation methodology. This study was done upon the request of synthetic vitamin E manufacturers to test the trace metal purity of their samples. In this work, the comparison of an acid microwave digestion and emulsion preparation is discussed. Cromium, nickel, tin and lead were found in the synthetic vitamin E analyzed and 200, 60, 9 and 45 ppb were the concentrations found respectively for these elements.Digesting the samples gives slightly lower detection limits compared to the emulsion preparation. 相似文献