Identification and Implementation of Biocatalytic Transformations in Route Discovery: Synthesis of Chiral 1,3-Substituted Cyclohexanone Building Blocks

Several biocatalytic approaches for the preparation of optically pure methyl 3-oxocyclo­hexane­carboxylates (<i>S</i>)-, (<i>R</i>)-<b>1</b> and 3-oxocyclo­hexane­carbo­nitriles (<i>S</i>)-, (<i>R</i>)-<b>2</b> have been successfully demonstrated. Screening of reaction-focused enzyme collections was used to identify initial hits using three enzymatic strategies. Reaction optimization and scale-up enabled the production of chiral intermediates for route scouting efforts on scales of up to 100 g. The enzymes applied in these processes (lipases, enoate reductases, and nitrilases) have been shown to be robust catalysts for drug manufacturing and represent a green alternative to conventional methods to access these chiral cyclohexanone building blocks

A case study of using Raman lidar measurements in high-accuracy GPS applications

International audienceThis paper investigates the impact of rapid small-scale water vapor fluctuations on GPS height determination. Water vapor measurements from a Raman lidar are used for documenting the water vapor heterogeneities and correcting GPS signal propagation delays in clear sky conditions. We use data from four short observing sessions (6 h) during the VAPIC experiment (15 May–15 June 2004). The retrieval of wet delays from our Raman lidar is shown to agree well with radiosonde retrievals (bias and standard deviation (SD) were smaller than 1 and 2.8 mm, respectively) and microwave radiometers (from two different instruments, bias was 6.0/−6.6 mm and SD 1.3/3.8 mm). A standard GPS data analysis is shown to fail in accurately reproducing fast zenith wet delay (ZWD) variations. The ZWD estimates could be improved when mean post-fit phase residuals were removed. Several methodologies for integrating zenith lidar observations into the GPS data processing are also presented. The final method consists in using lidar wet delays for correcting a priori the GPS phase observations and estimating a scale factor for the lidar wet delays jointly with the GPS station position. The estimation of this scale factor allows correcting for a mis-calibration in the lidar data and provides in the same way an estimate of the Raman lidar instrument constant. The agreement of this constant with an independent determination using radiosonde data is at the level of 1–4%. The lidar wet delays were derived by ray-tracing from zenith pointing measurements: further improvement in GPS positioning is expected from slant path lidar measurements that would properly account for water vapor anisotropy