Zeeman spectroscopy and crystal-field analysis of low symmetry centres in Nd3+doped Y2SiO5.

We report on infrared to visible Zeeman absorption spectroscopy and parameterised crystal-field modelling of Nd3+centres in Y2SiO5through the use of experimentally inferred crystal-field energy levels and Zeeman directional electronicgvalues. We demonstrate that good agreement between the calculated and experimental crystal-field energy levels as well as directional Zeemangvalues along all three crystallographic axes can be obtained. Further, we demonstrate that the addition of correlation crystal field effects successfully account for discrepancies that arise between the calculated and experimental values relevant to the2H11/2(2) multiplet in a one-electron crystal field model.

Zeeman and laser site selective spectroscopy of C1point group symmetry Sm3+centres in Y2SiO5: a parametrized crystal-field analysis for the 4f5configuration.

Parametrized crystal-field analyses are presented for both the six and seven fold coordinated, C1symmetry Sm3+centres in Y2SiO5, based on extensive spectroscopic data spanning the infrared to optical regions. Laser site-selective excitation and fluorescence spectroscopy as well as Zeeman absorption spectroscopy performed along multiple crystallographic directions has been utilized, in addition to previously determinedgtensors for the6H5/2Z1and4G5/2A1states. The resultant analyses give good approximation to the experimental energy levels and magnetic splittings, yielding crystal-field parameters consistent with the few other lanthanide ions for which such analyses are available.

Extending Phenomenological Crystal-Field Methods to C_{1} Point-Group Symmetry: Characterization of the Optically Excited Hyperfine Structure of

We show that crystal-field calculations for C_{1} point-group symmetry are possible, and that such calculations can be performed with sufficient accuracy to have substantial utility for rare-earth based quantum information applications. In particular, we perform crystal-field fitting for a C_{1}-symmetry site in ^{167}Er^{3+}:Y_{2}SiO_{5}. The calculation simultaneously includes site-selective spectroscopic data up to 20 000 cm^{-1}, rotational Zeeman data, and ground- and excited-state hyperfine structure determined from high-resolution Raman-heterodyne spectroscopy on the 1.5 µm telecom transition. We achieve an agreement of better than 50 MHz for assigned hyperfine transitions. The success of this analysis opens the possibility of systematically evaluating the coherence properties, as well as transition energies and intensities, of any rare-earth ion doped into Y_{2}SiO_{5}.

Electron paramagnetic resonance enhanced crystal field analysis for low point-group symmetry systems: C2v sites in Sm3+:CaF2/SrF2.

We present a comprehensive spectroscopic study of C[Formula: see text] point-group symmetry sites in Sm[Formula: see text]:CaF[Formula: see text]/SrF[Formula: see text] codoped with either NaF or LiF. Data includes electron paramagnetic resonance measurements of Zeeman and hyperfine interactions for the ground state, as well as site-selective excitation and fluorescence spectroscopy up to the [Formula: see text]G[Formula: see text] multiplet. Inclusion of the EPR data allowed us to determine unique crystal-field parameters. The parameters provide information about the geometry of the sites and the nature of the interactions between the Sm[Formula: see text] dopant and the alkaline earth co-dopant.

Evidence That the Anomalous Emission from CaF2:Yb2+ Is Not Described by the Impurity Trapped Exciton Model.

Yb-substituted CaF2 exhibits an anomalous red-shifted luminescence after UV excitation, attributed to the relaxation of impurity trapped excitons (ITE). CaF2:Yb is the archetype system for this model, in which the Yb2+ ions can be excited into a long-lived (ms) exciton state. Upon de-excitation, the emission intensity should be proportional to the Yb2+ concentration, but that could not be checked when this model was first proposed. Using the X-ray absorption near edge structure (XANES) technique, we determine the fractions of Yb2+ and Yb3+ for low Yb concentrations, 0.01% to 0.1%, and thus determine the net concentration of Yb2+. A comparison with luminescence data shows that the intensity is not proportional to the Yb2+ concentration, and only a fraction of Yb2+ ions contributes to the anomalous luminescence. This is inconsistent with the ITE model and illustrates the importance of checking the dependence of the emission intensity on the Yb2+ concentration.

Pressure dependence of the emission in CaF2 : Yb(2+).

We present a detailed spectroscopic investigation of CaF2 doped with Yb(2+) performed at high hydrostatic pressure which is applied in a diamond anvil cell. At ambient pressure and at temperatures lower than 175 K, the luminescence consists of a single broad band peaked at 18 500 cm(-1), attributed to the recombination of impurity-trapped excitons. Increasing pressure causes the luminescence to be observable at higher temperature. At a pressure of 72 kbar luminescence can be observed up to 275 K. The emission lineshape does not strongly depend on pressure below 85 kbar. However, at 85 kbar it is blue shifted to 21 630 cm(-1). This is attributed to the known phase transition of the CaF2 crystal from cubic to the orthorhombic phase. The absolute energy of the ground and 4f(13)5d states of Yb(2+) as well as the energy of the impurity-trapped exciton with respect to valence and conduction bands have been estimated. The results, are discussed in comparison with the pressure dependences observed for the luminescence of BaF2 : Eu(2+) and CaF2 : Eu(2+). The difference between the spectral properties of Eu(2+) and Yb(2+) is attributable to the fact that the ground and 4f(6)5d states of Eu(2+) are placed deeper in the CaF2 bandgap than the ground and excited 4f(13)5d states of Yb(2+), whereas the energies of the impurity-trapped exciton states for Yb(2+) and Eu(2+) with respect to the conduction band are approximately the same.

Reappearance of fine structure as a probe of lifetime broadening mechanisms in the 4f(N) --> 4f(N-1)5d excitation spectra of Tb3+, Er3+, and Tm3+ in CaF2 and LiYF4.

High-energy transitions in the 4f(N) -->4f(N-1)5d excitation spectra of lanthanide ions in host crystals are usually broadened due to the short excited-state lifetimes, whereas low-energy transitions, with longer excited-state lifetimes, may show fine structure. We report the surprising observation that for some materials fine structure is observed not only for the low-energy excitation bands but also for some high-energy transitions. The excited states that display fine structure are those for which the 5d electron is in the lowest crystal-field level but the 4f(N-1) core is in a highly excited state, indicating that the broadening depends only on the energy of the 5d electron and not on the total energy of the 4f(N-1)5d excited state.

Wound infiltration with local anaesthetic after abdominal hysterectomy.

The study was performed to investigate if wound infiltration with 20 ml of 0.5% bupivacaine after abdominal hysterectomy improved analgesia and reduced morphine requirements from a patient-controlled analgesia system during the first 6 h after operation. Forty patients undergoing abdominal hysterectomy were allocated randomly to one of two groups. The study was performed in a double-blind controlled manner. Morphine requirements in the first 6 h after operation were similar in both the control (30.3 mg) and bupivacaine (29.0 mg) groups. Cumulative hourly morphine requirements did not differ significantly between the two groups. Pain scores assessed by visual analogue were similar in both groups.

Splenic artery aneurysm rupture in pregnancy.

A multigravid patient was admitted at 34 weeks with abdominal pain, signs of hypovolaemia and an intrauterine death. Ultrasonography and paracentesis revealed bleeding into the peritoneal cavity. The diagnosis of splenic artery aneurysm rupture was considered. Energetic resuscitation and a multidisciplinary approach to surgery allowed a sacular splenic artery aneurysm to be tied off with preservation of both the spleen and the mother's life.

Molecular characterization of microbial alcohol dehydrogenases.

There is an astonishing array of microbial alcohol oxidoreductases. They display a wide variety of substrate specificities and they fulfill several vital but quite different physiological functions. Some of these enzymes are involved in the production of alcoholic beverages and of industrial solvents, others are important in the production of vinegar, and still others participate in the degradation of naturally occurring and xenobiotic aromatic compounds as well as in the growth of bacteria and yeasts on methanol. They can be divided into three major categories. (1) The NAD- or NADP-dependent dehydrogenases. These can in turn be divided into the group I long-chain (approximately 350 amino acid residues) zinc-dependent enzymes such as alcohol dehydrogenases I, II, and III of Saccharomyces cerevisiae or the plasmid-encoded benzyl alcohol dehydrogenase of Pseudomonas putida; the group II short-chain (approximately 250 residues) zinc-independent enzymes such as ribitol dehydrogenase of Klebsiella aerogenes; the group III "iron-activated" enzymes that generally contain approximately 385 amino acid residues, such as alcohol dehydrogenase II of Zymomonas mobilis and alcohol dehydrogenase IV of Saccharomyces cerevisiae, but may contain almost 900 residues in the case of the multifunctional alcohol dehydrogenases of Escherichia coli and Clostridium acetobutylicum. The aldehyde/alcohol oxidoreductase of Amycolatopsis methanolica and the methanol dehydrogenases of A. methanolica and Mycobacterium gasti are 4-nitroso-N,N-dimethylaniline-dependent nicotinoproteins. (2) NAD(P)-independent enzymes that use pyrroloquinoline quinone, haem or cofactor F420 as cofactor, exemplified by methanol dehydrogenase of Paracoccus denitrificans, ethanol dehydrogenase of Acetobacter and Gluconobacter spp. and the alcohol dehydrogenases of certain archaebacteria. (3) Oxidases that catalyze an essentially irreversible oxidation of alcohols, such as methanol oxidase of Hansenula polymorpha and probably the veratryl alcohol oxidases of certain fungi involved in lignin degradation. This review deals mainly with those enzymes for which complete amino acid sequences are available. The discussion focuses on a comparison of their primary, secondary, tertiary, and quaternary structures and their catalytic mechanisms. The physiological roles of the enzymes and isoenzymes are also considered, as are their probable evolutionary relationships.

Day-case herniotomy in children. A comparison of ilio-inguinal nerve block and wound infiltration for postoperative analgesia.

Forty-nine boys scheduled for day-case inguinal herniotomy were studied to compare ilio-inguinal nerve block and wound infiltration for postoperative analgesia. Both techniques were simple to perform and produced no complications. In the ilio-inguinal block group, 100% had either no pain or very mild discomfort when assessed 60 minutes after return to the day unit, compared to 95% in the infiltration group. Some children did appear to have pain following discharge but in all cases this responded well to simple analgesics. We conclude that both techniques provide satisfactory analgesia whilst the complications of narcotics are avoided, and suggest that simple infiltration of the wound with local anaesthetic solution should be encouraged in paediatric anaesthesia.