Neutral bis(pentafluorophenyl)triphenylarsinegold(III) complexes

The complexes XAu(C₆F₅)₂AsPh₃ have been prepared by substitution of chloro- or perchlorato-bis(pentafluorophenyl)triphenylarsinegold(III) with alkali or with silver salts MX (X = NO₃, CH₃COO, NO₂, CF₃COO, CN, SCN, N₃ and C₆H₅COO). Decomposition of the nitrato or acetato complex leads to C₆F₅AuAsPh₃.     

Internal fundamental sequences and approximative retracts

We introduce the notion of internal fundamental sequence and prove that any shape morphism from an arbitrary compactum X to an internally movable compactum Y is induced by an internal fundamental sequence. We use this special kind of fundamental sequences to give characterizations and some properties of AANR_C-sets and AANR_N-sets. The paper ends with a section devoted to internal FANR's.     

Group 11 complexes with the bis(3,5-dimethylpyrazol-1-yl)methane ligand. How secondary bonds can influence the coordination environment of Ag(I): the role of coordinated water in [Ag2(mu-L)2(OH2)2](OTf)2

The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane (L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 (1), with crystallographic mirror symmetry, or dinuclear [Ag2(mu-L)2](OTf)2 (2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 (3); Ag, X = OTf 4). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf (5). The gold(I) derivative [Au2(C6F5)2(mu-L)] (6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1-4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.     

Binary-black-hole encounters, gravitational bursts, and maximum final spin

The spin of the final black hole in the coalescence of nonspinning black holes is determined by the "residual" orbital angular momentum of the binary. This residual momentum consists of the orbital angular momentum that the binary is not able to shed in the process of merging. We study the angular momentum radiated, the spin of the final black hole, and the gravitational bursts in a sequence of equal mass encounters. The initial orbital configurations range from those producing an almost direct infall to others leading to numerous orbits before infall, with multiple bursts of radiation. Our sequence consists of orbits with fixed impact parameter. What varies is the initial linear momentum of the black holes. For this sequence, the final black hole of mass M_{h} gets a maximum spin parameter a/M_{h} approximately 0.823, with this maximum occurring for initial orbital angular momentum L/M_{h};{2} approximately 1.176.     

Silica xerogels of tailored porosity as support matrix for optical chemical sensors. Simultaneous effect of pH, ethanol:TEOS and water:TEOS molar ratios, and synthesis temperature on gelation time, and textural and structural properties

The sensing of a chemical environment is achieved mainly in the surface by interactions of the sensor material with its chemical surroundings. Therefore, porous structure control is key in developing good chemical sensors. The aim of this work was to obtain materials of tailored porosity to be used as support matrix for optical chemical sensors. We studied the simultaneous effect of pH, temperature, ethanol:TEOS, and water:TEOS molar ratios on gelation time, and textural and structural properties. We used a 2⁴ factorial design that evaluates the effect of each independent variable and their interactions. Samples were characterized by XRD, SEM, FTIR, and gas adsorption (N₂ at 77 K and CO₂ at 273 K). The gelation time decreased with increasing temperature, water:TEOS molar ratio, and pH; and with decreasing ethanol:TEOS molar ratios. Synthesis conditions also affected the xerogels porous textures. Xerogels obtained at pH 2.5 were ultramicroporous. In general, samples synthesized at pH 4.5 and ethanol:TEOS molar ratio of 2.25:1 were mesoporous, but the material is not appropriate for use as support in fiber optical sensors.     

Novel dithiolene complexes incorporating conjugated electroactive ligands

A series of new metal (M) dithiolene complexes bearing terthiophene (3, 12, M = Ni; 4, M = Pd; 5, 6, M = Au) and 2,5-bis(para-methoxyphenyl)thiophene units (14, M = Ni; 15, 16, M = Au; 17, M = Pd) have been synthesised in 38-99% yield. The electrochemical properties of the materials have been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry. The nickel complexes possess low oxidation potentials (-0.12 to -0.25 V vs Ag/AgCl) due to the electron-rich dithiolene centres and all complexes display ligand-based redox activity. The terthiophene derivatives have been polymerised by electrochemical oxidation to give stable films with, in the case of poly(3), broad absorption characteristics. Charge transfer materials have been isolated from 14 and 16 with conductivities in the range 9 x 10(-6) to 7 x 10(-8) S cm(-1).     

Vapochromic behavior of {Ag2(Et2O)2[Au(C6F5)2]2}n with volatile organic compounds

The vapochromic behaviors of {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1), Me2CO (2), THF (3), CH3CN (4)) were studied. {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1)) was synthesized by the reaction of [Bu4N][Au(C6F5)2] with AgOClO3 in 1:1 molar ratio in CH2Cl2/Et2O (1:2). 1 was used as starting material with THF to form {Ag2L2[Au(C6F5)2]2}n (L = THF (3)). 3 crystallizes in the monoclinic space group C2/c and consists of tetranuclear units linked together via aurophilic contacts resulting in the formation of a 1D polymer that runs parallel to the crystallographic z axis. The gold(I) atoms are linearly coordinated to two pentafluorophenyl groups and display additional Au...Ag close contacts within the tetranuclear units with distances of 2.7582(3) and 2.7709(3) A. Each silver(I) center is bonded to the two oxygen atoms of the THF molecules with a Ag-O bond distance of 2.307(3) A. TGA analysis showed that 1 loses two molecules of the coordinated solvent per molecular unit (1st one: 75-100 degrees, second one: 150-175 degrees C), whereas 2, 3, and 4 lose both volatile organic compounds (VOCs) and fluorinated ligands in a less well defined manner. Each complex loses both the fluorinated ligands and the VOCs by a temperature of about 325 degrees C to give a 1:1 gold/silver product. X-ray powder diffraction studies confirm that the reaction of vapors of VOCs with 1 in the solid state produce complete substitution of the ether molecules by the new VOC. The VOCs are replaced in the order CH3CN > Me2CO > THF > Et2O, with the ether being the easiest to replace. {Ag2(Et2O)2[Au(C6F5)2]2}n and {Ag2(THF)2[Au(C6F5)2]2} n both luminesce at room temperature and at 77 K in the solid state. Emission maxima are independent of the excitation wavelength used below about 500 nm. Emission maxima are obtained at 585 nm (ether) and 544 nm (THF) at room temperature and at 605 nm (ether) and 567 nm (THF) at 77 K.     

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.