Biosynthetic Studies on Antibiotics

The intricacies of the synthetic chemistry executed by living cells in the assembly of complex organic natural products can be probed in great detail by stable-isotope labeling in conjunction with sophisticated 2D and multiple-quantum NMR methods of analysis. Mechanistic details are revealed by unraveling the “cryptic” stereochemistry of biosynthetic reactions with the aid of stereospecific isotope labeling. Analysis of blocked mutants and cloning of biosynthetic genes provides new tools for the study of biosynthetic pathways and for the exploitation of the chemical capabilities of living organisms.     

Unraveling the crystallization mechanism of CoAPO-5 molecular sieves under hydrothermal conditions

The hydrothermal crystallization of CoAPO-5 molecular sieves has been studied using time-resolved in-situ SAXS/WAXS, UV-vis, Raman, and XAS. Data collected during heating to 180 degrees C allowed the observation of different steps occurring during the transformation of the amorphous gel into a crystalline material from a macroscopic and atomic perspective. Raman spectroscopy detected the initial formation of Al-O-P bonds, whereas SAXS showed that these gel particles had a broad size distribution ranging from ca. 7 to 20 nm before crystallization began. WAXS showed that this crystallization was sharp and occurred at around 160 degrees C. Analysis of the crystallization kinetics suggested a one-dimensional growth process. XAS showed that Co(2+) transformed via a two-stage process during heating involving (i) a gradual transformation of octahedral coordination into tetrahedral coordination before the appearance of Bragg peaks corresponding to AFI, suggesting progressive incorporation of Co(2+) into the poorly ordered Al-O-P network up to ca. 150 degrees C, and (ii) a rapid transformation of remaining octahedral Co(2+) at the onset of crystallization. Co(2+) was observed to retard crystallization of AFI but provided valuable information regarding the synthesis process by acting as an internal probe. A three-stage, one-dimensional crystallization mechanism is proposed: (i) an initial reaction between aluminum and phosphate units forming a primary amorphous phase, (ii) progressive condensation of linear Al-O-P chains forming a poorly ordered structure separated by template molecules up to ca. 155 degrees C, and (iii) rapid internal reorganization of the aluminophosphate network leading to crystallization of the AFI crystal structure.     

Microfabricated bioreactor chips for immobilised enzyme assays

A microfabricated device is reported that has been designed to permit the in situ packing of a section of channel with enzyme immobilised onto controlled pore glass (CPG). It is fabricated from glass and polydimethylsiloxane and to prevent dead volumes, has dedicated channels for packing the reactor. The device has the advantage of being simple in design, the flow through enzyme reactor channel being simply a widened section of the analyte channel. The system is suitable for both hydrodynamic and electro-osmotic pumping, and is designed such that when the packing is exhausted it can be repacked. Controlled pore glass provides a reproducible none swelling, high porosity medium onto which the enzyme could be immobilised. The large particle size meant that it was vital to optimise the immobilisation procedure in order to achieve acceptable enzyme activity. The microfabricated device was developed with two enzymes of different molecular masses; alkaline phosphatase and xanthine oxidase. The pore size of the CPG was found to be very important for xanthine oxidase, where the 697 Å pore size (120-200 mesh) CPG was found to give the highest activity (18-20% activity retained after immobilisation). The microfabricated device was used for the assay of p-nitrophenyl phosphate and hypoxanthine with spectrophotometric detection at 405 and 470 nm, respectively. The limits of detection were 5 and 8 μM, respectively.     

对一个大单轴磁各向异性镍(Ⅱ)配合物中的磁跃迁的直接观察

最近Ruamps和同事发现三角双锥构型的Ni（Ⅱ）配合物[Ni（Me₆tren）Cl]ClO₄（1，Me₆tren=tris（2-（dimethylamino）ethyl）amine）具有大的单轴磁各向异性（J.Am.Chem.Soc.，2013，135：3017-3026）。他们利用HF-EPR研究获得横向零场分裂（ZFS）参数E=1.56（5）cm^-1但未能确定轴向零场分裂参数D。在本工作中，我们利用0~17.5 T和5 K的变磁场远红外光谱（FIRMS）来检测自旋基态S=1中的M_S=±1和M_S=0态之间的磁跃迁。在FIRMS中直接观察到Zeeman分裂态之间的跃迁，得出轴向ZFS参数D=-110.7（3）cm^-1。我们对1的晶体结构进行了Hirshfeld表面分析，揭示了1分子中的阳离子与阴离子之间以及分子之间的相互作用。     

Spectral baseline ripple in hot-electron bolometer mixers due to local oscillator phase and amplitude instabilities

High resolution millimetre and submillimetre wave astronomical spectrometers using hot-electron bolometer mixers as detectors often show marked standing wave patterns in the spectral baseline. LO phase noise contributes through two mechanisms: the phase noise side-bands may be converted to amplitude noise in the source because of the power-frequency characteristic of the source, or they can be converted to in-band amplitude noise through the action of the quasi-optical discriminator formed by the mixer, beam-splitter and telescope structure. The baseline ripple components due to each of these mechanisms have different characteristic periods, and under some circumstances can dominate the spectrometer baseline. The ripple levels estimated using the theory agree well with those observed in practice. It is shown that with careful design systematic effects due to this cause can be reduced to a negligible level.     

VSWR reduction for large millimeter-wave cassegrain radiotelescopes

Multiple reflections in large radiotelescopes used for astronomical spectroscopy cause characteristic modulations of the observed spectrum (baseline ripple). For a given mechanism, the magnitude of the effect depends primarily on the reflection coefficient, which for the most important paths is proportional to . Although ripple is thus generally negligible at mm-wavelengths, there are some instances where it may still be significant, and a recent experiment at the15 m James Clerk Maxwell Telescope was severely affected. We describe a technique which has proved effective in reducing the ripple to an acceptable level.The purpose of this research note is to draw this technique to the attention of the astronomical community. We calculate the reflection coefficient for a typical instrument and show that it can be greatly reduced over a very broad bandwidth by means of a tapered absorber in the centre of the secondary mirror. The graphical analysis of the tapered absorber also demonstrates that the scattering cones and circular absorbers widely used in radioastronomy donot in fact reduce the reflection coefficient significantly.