Chemoenzymatic Asymmetric Synthesis of Pyridine-Based α-Fluorinated Secondary Alcohols

Fluoro-substituted and heteroaromatic compounds are valuable intermediates for a variety of applications in pharma- and agrochemistry and synthetic chemistry. This study investigates the chemoenzymatic preparation of chiral alcohols bearing a heteroaromatic ring with an increasing degree of fluorination in α-position. Starting from readily available picoline derivatives prochiral α-halogenated acyl moieties were introduced with excellent selectivity and 64–95 % yield. The formed carbonyl group was subsequently reduced to the corresponding alcohols using the alcohol dehydrogenase from Lactobacillus kefir, yielding an enantiomeric excess of 95–>99 % and up to 98 % yield.     

Hot corrosion Type II of FeCr‐based model alloys for boiler and heat exchanger applications

The hot corrosion Type II of the alloys FeCr20, FeCr20Ni10, FeCr20Ni20, and FeCr20Co10 is investigated at 700°C in air + 0.5% SO₂ with deposits consisting of Na₂SO₄ and a eutectic mixture of Na₂SO₄ and MgSO₄ for 24, 100, and 300 h. The alloying elements nickel and cobalt have a positive influence when tests are conducted using a MgSO₄‐Na₂SO₄ deposit. In this case, they reduce the metal loss and increase the time to the propagation stage. In contrast, when the alloys are exposed with a Na₂SO₄ deposit, these alloying elements increase the metal loss and allow for the transition to the propagation stage because they can form molten phases with the Na₂SO₄. During the incubation stage an oxide scale forms on the FeCr20 alloy, which is thicker than the one formed during exposure without a deposit, and iron oxides are observed, which precipitate in the deposit. The propagation stage occurs by a dissolution and precipitation mechanism forming localized pitting attack. Iron is the main species that dissolves and precipitates, while chromium remains mainly as an oxide beneath the initial surface. The additional elements are found in the pit and in the salt deposit.     

Effects of alloy additions on the microstructures and tensile properties of cast Co-Cr-Mo alloy used for surgical implants

The composition of the Co-Cr-Mo alloy has been modified by additions of nickel and some trace elements aluminium, titanium and boron. In this paper, the first part of the present study, the effects of alloy additions on the microstructures and tensile properties of the as-cast Co-Cr-Mo alloy are discussed. The effects of alloy additions on the fatigue behaviour of the alloy will be discussed in the second part of the present study. It is found that alloy additions do not seem to result in changes in the nature of the casting structure. A directional, coarse dendritic cast structure is produced in the modified alloys as in the base alloY. However, the alloy additions affect the carbide precipitations and the formation of some fine details of the microstructure such as dislocations, stacking faults and twins produced during the solidification. A considerable improvement in the transient mechanical properties, especially in the tensile ductility, is achieved by modifying the base alloy with alloy additions.     

Higher Order Barycentric Coordinates

In recent years, a wide range of generalized barycentric coordinates has been suggested. However, all of them lack control over derivatives. We show how the notion of barycentric coordinates can be extended to specify derivatives at control points. This is also known as Hermite interpolation. We introduce a method to modify existing barycentric coordinates to higher order barycentric coordinates and demonstrate, using higher order mean value coordinates, that our method, although conceptually simple and easy to implement, can be used to give easy and intuitive control at interactive frame rates over local space deformations such as rotations.     

Nitric oxide reduction at noble metal electrodes: a voltammetric study in acid solution

Features of the electrochemical reduction of nitric oxide on platinum, palladium, rhodium and ruthenium in aqueous perchloric acid solutions (0.33–1.0 M) are compared. The results from voltammetric studies (ie linear potential sweep and rotating disc electrode) using the bulk metal electrodes are described and compared with residual current voltage plots in acid electrolyte alone. In general, three nitric oxide reduction peaks are observed on the metals. The most anodic peak, at ca E = 0.15 V vs sce is attributed to the one-electron reduction of nitric oxide to an adsorbed NOH intermediate on a bare metal surface (ie one free of oxides or adsorbed hydrogen). The other two peaks occur in potential regions where adsorbed hydrogen is present on the metal surface (ca E = 0.0 and −0.20 V, respectively). The co-adsorbed hydrogen complicates the analysis and precludes an unambiguous interpretation of these two peaks. However, they apparently reflect nitric oxide reduction to nitrogen, hydroxylamine and/or ammonia. In a cathodic scan on the rhodium electrode, a current plateau is seen instead of the first (most anodic) peak, a probable consequence of oxide film formation with subsequent chemical complications. On the ruthenium electrode the first two (most anodic) peaks are not observed probably due to a relatively stable oxide layer. Reaction selectivities at metal black gas diffusion cathodes operating in an electrogenerative (ie galvanic) mode with perchloric acid electrolyte are compared with the voltammetric results at the corresponding bulk electrodes. Dinitrogen formation is observed on the platinum and rhodium black electrodes as suggested from voltammetric results. A series-parallel reaction sequence is proposed to explain the results. Limitations of using simple voltammetric techniques for predicting behavior of large scale preparative electrochemical reactors are discussed.     

Multicenter study on the clinical value of fetal pulse oximetry. I. Methodologic evaluation. The French Study Group on Fetal Pulse Oximetry

OBJECTIVE: Our purpose was to evaluate the feasibility of intrapartum fetal pulse oximetry, the distribution of fetal oxygen saturation values, and the relationship with the neonatal outcome in a population with an abnormal fetal heart rate. STUDY DESIGN: A prospective multicenter observational study was performed from June 1994 to November 1995. Fetal oxygen saturation was continuously recorded with use of a Nellcor N-400 fetal pulse oximeter in case of an abnormal fetal heart rate during labor. Simultaneous readings of fetal oxygen saturation and fetal blood analysis were obtained at inclusion and before birth. Feasibility, adverse effects, distribution of fetal oxygen saturation values, and relationship with neonatal outcome were assessed. RESULTS: One hundred seventy-four patients were included. From 172 attempted sensor placements, the procedure was impossible in three cases and fetal oxygen saturation values were obtained in 164 cases (95.3%). Physicians considered sensor placement an easier task than an attempt at fetal blood analysis (easy in 87.5% vs 78.9% for fetal blood analysis, p = 0.03). The mean reliable signal time (+/- SD) was 64.7% +/- 32% during the first stage. There were no serious adverse effects in the study population. The mean fetal oxygen saturation during the first stage of labor was 42.2% +/- 8.0% (10th to 90th percentile range 30% to 53%). Fetal oxygen saturation was significantly correlated with scalp pH (r = 0.29, p = 0.01) but not with neonatal umbilical artery pH or gas values. There was a significant association between low fetal oxygen saturation (< 30%) and poor neonatal condition. CONCLUSION: The feasibility of fetal pulse oximetry is satisfactory in clinical practice. It is easy to use and provides a fair rate of recorded values, even in a population with suspicion of fetal distress. A low fetal oxygen saturation is significantly associated with an abnormal neonatal outcome.