Engineering of Yeast Old Yellow Enzyme OYE3 Enables Its Capability Discriminating of (E)-Citral and (Z)-Citral

The importance of yeast old yellow enzymes is increasingly recognized for direct asymmetric reduction of (E/Z)-citral to (R)-citronellal. As one of the most performing old yellow enzymes, the enzyme OYE3 from Saccharomyces cerevisiae S288C exhibited complementary enantioselectivity for the reduction of (E)-citral and (Z)-citral, resulting in lower e.e. value of (R)-citronellal in the reduction of (E/Z)-citral. To develop a novel approach for the direct synthesis of enantio-pure (R)-citronellal from the reduction of (E/Z)-citral, the enzyme OYE3 was firstly modified by semi-rational design to improve its (R)-enantioselectivity. The OYE3 variants W116A and S296F showed strict (R)-enantioselectivity in the reduction of (E)-citral, and significantly reversed the (S)-enantioselectivity in the reduction of (Z)-citral. Next, the double substitution of OYE3 led to the unique variant S296F/W116G, which exhibited strict (R)-enantioselectivity in the reduction of (E)-citral and (E/Z)-citral, but was not active on (Z)-citral. Relying on its capability discriminating (E)-citral and (Z)-citral, a new cascade reaction catalyzed by the OYE3 variant S296F/W116G and glucose dehydrogenase was developed, providing the enantio-pure (R)-citronellal and the retained (Z)-citral after complete reduction of (E)-citral.     

硅胶负载手性氨基醇聚合物的合成及其应用

以L-亮氨酸(L-Leu)为手性源,经酯化、格氏化、酰胺化等步骤制备手性单体(L-NALAA),以该单体为手性识别基团,在引发剂偶氮二异丁腈和交联剂乙二醇二甲基丙烯酸酯(EDMA)的作用下,与烯化功能硅胶发生自由基共聚反应,制备了新型键合硅胶手性固定相,其结构经FT-IR、TGA、EA表征。以4种对映异构体为模型药物对手性材料手性固定相的手性拆分性能进行研究,结果表明,手性材料手性固定相对奥美拉唑和兰索拉唑的拆分效果较好。     

An Efficient Stereoselective Synthesis of Key Fragments of Elaiophylin

The stereoselective synthesis of key fragments 3 and 7 of elaiophylin has been accomplished from readily available epichlorohydrin as the starting material. The key reactions involved are Jacobsen's kinetic resolution, Prins cyclization, pyridinium chlorochromate‐mediated oxidative cleavage, Grignard reaction, and cross‐metathesis reaction.     

Negative ion electrospray high‐resolution tandem mass spectrometry of polyphenols

Representative compounds with a 1,3‐dihydroxybenzene substructure belonging to different important polyphenol classes (stilbenes, flavones, isoflavones, flavonols, flavanones, flavanols, phloroglucinols, anthraquinones and bisanthraquinones) were investigated based on detailed high‐resolution tandem mass spectrometry measurements with an Orbitrap system under negative ion electrospray conditions. The mass spectral behaviour of these compound classes was compared among each other not only with respect to previously described losses of CO, CH₂CO and C₃O₂ but also concerning the loss of CO₂ and successive specific fragmentations. Furthermore, some unusual fragmentations such as the loss of a methyl radical during mass spectral decomposition are discussed. The obtained results demonstrate both similarities and differences in their mass spectral fragmentation under MSⁿ conditions, allowing a characterization of the corresponding compound type. Copyright © 2015 John Wiley & Sons, Ltd.     

Optimisation of an EPR dosimetry system for robust and high precision dosimetry

Clinical applications of electron paramagnetic resonance (EPR) dosimetry systems demand high accuracy causing time consuming analysis. The need for high spatial resolution dose measurements in regions with steep dose gradients demands small sized dosimeters. An optimization of the analysis was therefore needed to limit the time consumption. The aim of this work was to introduce a new smaller lithium formate dosimeter model (diameter reduced from standard diameter 4.5 mm to 3 mm and height from 4.8 mm to 3 mm). To compensate for reduced homogeneity in a batch of the smaller dosimeters, a method for individual sensitivity correction suitable for EPR dosimetry was tested. Sensitivity and repeatability was also tested for a standard EPR resonator and a super high Q (SHQE) one. The aim was also to optimize the performance of the dosimetry system for better efficiency regarding measurement time and precision. A systematic investigation of the relationship between measurement uncertainty and number of readouts per dosimeter was performed. The conclusions drawn from this work were that it is possible to decrease the dosimeter size with maintained measurement precision by using the SHQE resonator and introducing individual calibration factors for dosimeter batches. It was also shown that it is possible reduce the number of readouts per dosimeter without significantly decreasing the accuracy in measurements.     

Epitaxial growth of Ge1-xSnx films with x up to 0.14 grown on Ge （001） at low temperature

We characterize the structures of Ge1-xSnx films with x up to 0.14 grown on Ge （001） by molecular-beam epitaxy at low temperature. The results show that Ge1-xSnx films are fully strained even at high Sn composition. The in-plane lattice parameters remain exactly the same as that of the substrate. Depth sensitivity analysis of the lattice parameters indicates that the strains of the epitaxial films are all in homogeneity. The films are fully strained. Poisson ratios, the force constants for the bonds between Ge and Sn are estimated and discussed in the present paper. Raman results show Ge-Ge, Ge-Sn, Sn-Sn vibrational modes. The Sn-Sn bond aggregation may respond to the high quality of our films. The fully strained epitaxy films with high content of Sn may be useful in designing the high quality GeSn films.     

Angular reconstruction of a lead scintillating-fiber sandwiched electromagnetic calorimeter

The Neighbor Cell Deposited Energy Ratio （NCDER） is a new method that is proposed to reconstruct incidence position in a single layer for a 3-dimensional imaging electromagnetic calorimeter （ECAL）. This method was applied to reconstruct the ECAL test beam data for the Alpha Magnetic Spectrometer-02 （AMS-02）. The results show that this method can achieve an angular resolution of 7.36±0.08°/√E＋0.28±0.02° in the determination of the photon＇s direction, which is much more precise than that obtained with the commonly-adopted Center of Gravity （COG） method （8.4±0.1°/E＋0.8±0.3°）. Furthermore, since it uses only the properties of electromagnetic showers, this new method could also be used for other type of fine grain sampling calorimeters.     

Three‐dimensional visible‐light capsule enclosing perfect supersized darkness via antiresolution

Supersized darkness in three dimensions surrounded by all light in free space is demonstrated theoretically and experimentally in the visible regime. The object staying in the darkness is similar to staying in an empty light capsule because light just bypasses it by resorting to destructive interference. A binary‐optical system is designed and fabricated based on achieving antiresolution (AR), by which electromagnetic energy flux avoids and bends smoothly around a nearly perfect darkness region. AR remains an unexplored topic hitherto, in contrast to the super‐resolution for realizing high spatial resolution. This novel scheme replies on smearing out the point spread function and thus poses less stringent limitations upon the object's size and position since the created dark (zero‐field) area reach 8 orders of magnitude larger than λ² in cross‐sectional size. It functions very well with arbitrarily polarized beams in three dimensions, which is also frequency scalable in the whole electromagnetic spectrum.     

Relative angular precision in electron backscatter diffraction: A comparison between cross correlation and Hough transform based analysis

In the present study the relative angular resolution of an electron backscatter diffraction system based on Hough transform analysis has been determined with a silicon single crystal wafer. The resolution is found to be better than 0.1° and can be easily improved by repetition of measurements. A test measurement on a BaFe₂As₂ thin film, where disorientations of 0.1° and less are present, was performed using the cross correlation electron backscatter diffraction technique. The same measurement is evaluated with the Hough transform technique. Comparing both techniques give evidence of a relative resolution of better than 0.1°. However, in specimen areas with strain inhomogeneities a deviation along one rotation axis can be observed.