We introduce a protecting-group-free concept for the powerful para-fluoro-thiol reaction (PFTR) employing a source of fluoride ions as base. The reaction is shown to be self-propagating, with under-stoichiometric amounts of base, thus effectively foregoing the need for high base concentrations. Careful tuning of the solvent–thiol combination allows for quantitative conversion, in some cases within a short timeframe, when only minimal amounts of base are used, allowing the PFTR reaction to essentially proceed base-free. 相似文献
CW diode-pumped laser operation of Nd3+ in Ca3Sc2Ge3O12 (CaSGG) single garnet crystal has been demonstrated for the first time. We measured an 18% slope efficiency and 2.7-nm tunability
with two different laser cavities. A spectroscopic characterization of our sample has also been performed including the absorption
cross section in the 800-nm region and the emission cross section and radiative lifetime of the upper laser level.
Received: 7 December 1999 / Revised version: 6 February 2000 / Published online: 27 April 2000 相似文献
Visible optical properties of two crystalline fibers (KY3F10 and LiLuF4) doped with Dy3+ have been investigated. In particular, the room-temperature absorption spectra have been analyzed using the Judd–Ofelt theory and the intensity parameters have been obtained. A criterion suitable for determining the proper choice of the dopant composition to tailor the luminescence properties of the crystals is proposed. 相似文献
Transparent single crystals of erbium-doped LaVO4 in form of platelets having an average size 0.5×2×2 mm3 were obtained by the flux method using Pb2V2O7 as the solvent. Inductively coupled plasma (ICP) measurement revealed that the actual Er/La=0.3% molar ratio in the crystals is lower than Er/La=1% nominal molar ratio due to significant difference of ionic radii of La and Er. Luminescence spectra and luminescence decay curves for Er3+ transitions in the visible and near infrared region were recorded. Unpolarized Raman spectrum of undoped LaVO4 crystal was acquired, too. Up-converted green emission following excitation at 808 and 970 nm was observed and dependence of its intensity on incident excitation power was determined. Based on experimental data gathered the relaxation dynamics of excited states of Er3+ was analyzed and mechanisms involved in the up-conversion phenomena were discussed. 相似文献
An anti trihydroxycarbenium ion is revealed to be the gas‐phase structure of protonated carbonic acid by IR multiple‐photon dissociation spectroscopy (see picture for calculated structure and comparison of experimental and computed spectra). Deprotonation yields anti‐H2CO3 with a nominal gas‐phase basicity of 724 kJ mol?1.
Gaseous [C7H7O]+ ions have been formed by protonation of benzaldehyde or tropone (2,4,6-cycloheptatrienone) in the cell of an FT-ICR mass spectrometer using C2H5(+) as a Br?nsted acid. The so-formed species have been assayed by infrared multiphoton dissociation (IRMPD) using the free electron laser (FEL) at the CLIO (Centre Laser Infrarouge Orsay) facility. The IRMPD features are quite distinct for ions from the two different precursors, pointing to two different isomers. A number of potential structures for [C7H7O]+ ions have been optimized at the B3LYP/6-31+G(d,p) level of theory, and their relative energies and IR spectra are reported. On this basis, the IRMPD spectra of [C7H7O]+ ions are found to display features characteristic of O-protonated species, with no evidence of any further skeletal rearrangements. The so-formed ions are thus hydroxy-substituted benzylium and tropylium ions, respectively, representative members of the benzylium/tropylium ion family. The IRMPD assay using the FEL laser light has allowed their unambiguous discrimination where other mass spectrometric techniques have yielded a less conclusive answer. 相似文献
A generic method for the efficient in-situ modification of liposomes is described based on "click" chemistry, and a simple colorimetric assay is developed for monitoring the reaction. 相似文献
The complexes [Pd(eta2-dmfu)(P-N)] [P-N = 2-(PPh2)C6H4-1-CH=NR, R = C(6)H(4)OMe-4; CHMe2; C6H3Me2-2,6; C6H3(CHMe2)-2,6] react with an excess of BrC6H4R1-4 (R1= CF3; Me) yielding the oxidative addition products [PdBr(C6H4R1-4)(P-N)] at different rates depending on R [C6H4OMe-4 > C6H3(CHMe2)-2,6 > CHMe2 approximately C6H3Me2-2,6] and R1 (CF3> Me). In the presence of K2CO3 and activated olefins (ol = dmfu, fn), the latter compounds react with an excess of 4-R2C6H4B(OH)2 (R2= H, Me, OMe, Cl) to give [Pd(eta2-ol)(P-N)] and the corresponding biaryl through transmetallation and fast reductive elimination. The transmetallation proceeds via a palladium(II) intermediate with an O-bonded boron anion, the formation of which is markedly retarded by increasing the bulkiness of R. The intermediate was isolated for R = CHMe2, R1 = CF3 and R2= H. The boron anion is formulated as a diphenylborinate anion associated with phenylboronic acid and/or as a phenylboronate anion associated with diphenylborinic acid. In general, the oxidative addition proceeds at a lower rate than transmetallation and represents the rate-determining-step in the coupling reaction of aryl bromides with arylboronic acids catalyzed by [Pd(eta2-dmfu)(P-N)]. 相似文献