Synthesis of 2-D-L-tryptophan by sequential Ir-catalyzed reactions

Herein, we report a practical synthesis of 2-D-l-tryptophan via sequential Ir-catalyzed CH borylation, and Ir-catalyzed C-2-deborylative deuteration steps. In this synthetic sequence, deprotection of the Boc and methyl ester groups proved challenging, due to replacement of deuterium with hydrogen. However, mild deprotection conditions were developed to avoid this D/H scrambling. Further, 2-D-L-Tryptophan is stable in many buffers used for biological studies.     

Capillary array isoelectric focusing with laser-induced fluorescence detection: milli-pH unit resolution and yoctomole mass detection limits in a 32-channel system

We report a multiplexed capillary electrophoresis system employing an array of 32 capillaries with a micromachined sheath-flow cuvette as the detection chamber. The sample streams were simultaneously excited with a 473-nm laser beam, and the fluorescence emission was imaged on a CCD camera with a pair of doublet achromat lens. The instrument produced mass detection limits of 380 ± 120 yoctomoles for fluorescein in zone electrophoresis. Capillary isoelectric focusing of fluorescent standards produced peaks with an average width of 0.0029 ± 0.0008 pH. Capillary coating stability limits the reproducibility of the analysis.     

饱和铁芯型超导限流器对距离保护的影响

饱和铁芯型超导限流器SCFCL(Saturated Core Superconducting Fault Current Limiter)是一种较为理想的高电压限流器,利用其技术特点可以实现无时限的明显限流作用,有着广泛的运用前景。距离保护能够很好的满足高电压复杂网络快速、精确切除故障的要求,其主要元件阻抗继电器是现阶段普遍应用的高性能继保装置。SCFCL在高压输电网络的接入会对距离保护产生很大影响,运用PSCAD搭建500kV输电线路模型,详细分析限流器接入前后不同短路故障类型及故障距离对线路距离保护的影响。     

Direct Formic Acid Mediated Z‐Selective Reductive Coupling of Dienes and Aldehydes

Methods for the addition of unsaturated nucleophiles to carbonyls to generate Z‐olefin products remain rare and often require either alkyl borane or zinc reductants, limiting their utility. Demonstrated here is that formic acid mediates the Rh‐catalyzed, Z‐selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active Rh intermediate by ligand dissociation is the rate‐determining step. The rapid generation and trapping of Rh‐allyl intermediates is key to preventing chain‐walking isomerization events that plague related protocols. Insights gained through this study may have wider implications in selective metal‐catalyzed hydrofunctionalization reactions.     

基于能量函数的SMES优化布局研究

SMES的快速功率响应特性可以实现电力系统的主动致稳,为电力系统稳定问题提供有效的解决途径。分布式SMES的布局作为SMES应用过程中一个关键问题,是其在电力系统中实现工程化应用的重要技术课题。文中采用能量函数方法,对分布式SMES的布局问题进行研究。首先采用暂态能量函数法进行故障扫描,然后分析网络中暂态能量的分布特性,将电力系统的全局稳定性问题映射于网络局部的稳定性问题,确定系统的薄弱环节,在此基础上提出多机系统中的SMES优化布局方案。基于三机九母线系统模型进行仿真,验证了本方案的有效性。     

Low-temperature synthesis of porous hydroxyapatite scaffolds using polyaphron templates

A method to synthesize porous hydroxyapatite (HA) structures at a low temperature was investigated in this study. Polyaphrons, a class of high-internal-phase-ratio emulsions were used as the shape-directing template for the sol-gel reactions that facilitated the formation of the structures. Electron micrographs revealed a three dimensional porous structure with pore sizes in the range of 1–5 microns. X-ray diffraction images showed that the hydroxyapatite structure formed after treatment at 400°C matched exactly with commercial HA spectra indicating that the phase transformation was complete. IR spectra of the samples confirm the formation of the structural components characteristic of commercial HA.     

Molecular Aggregation of Naphthalene Diimide(NDI) Derivatives in Electron Transport Layers of Inverted Perovskite Solar Cells and Their Influence on the Device Performance

One of key factors to design applicable electron transport layers (ETLs) for perovskite solar cells is the morphology of ETLs since a good morphology would help to facilitate the carrier transport at two interfaces (perovskite\ETL and ETL\cathode). However, one drawback of most organic ETL small molecules is the internal undesired accumulation, which would cause the formation of inappropriate morphology and rough ETL surface. Here, by elaborately designing the side chains of NDI derivatives, the molecular interaction could be modified to achieve the aggregation in different degrees, which would eventually affect the accumulation of molecules and surface qualities of ETLs. By speculating from the comparison between the absorption spectra of solutions and films, the sequence of extent of molecule interaction and aggregation was built among three NDI derivatives, which is further confirmed by direct evidence of atomic force microscopy (AFM) images. Then, carrier exaction abilities are simply studied by steady‐state photoluminescence spectroscopy. The carrier transport process is also discussed based on cyclic voltammetry, time‐resolved photoluminescence spectroscopy and mobility. NDIF1 are proven to have the appropriate internal aggregation to smooth the contact with cathode and low series resistance, and a device performance of 15.6 % is achieved. With the ability of preventing the thermal diffusion of Ag towards the perovskite surface due to the strong interaction between molecules, NDIF2 at high concentration shows the highest fill factor (80 %).     

Synthesis and anticancer activity of novel NHC-gold(I)-sugar complexes

Gold(I) complexes containing stabilising ligands such as phosphines or N-heterocyclic carbenes (NHCs) are known to be inhibitors of the enzyme thioredoxin reductase (TrxR) and therefore act as potential apoptosis-inducing anticancer drug candidates. The conjugation of biomolecules overexpressed in cancer cells to the gold complexes makes them semi-targeted metabolites. Auranofin, an anti-arthritis agent, encompasses this property and exhibits anti-tumour activities. The synthesis, characterization and biological evaluation of four novel N-heterocyclic carbene-gold(I)-thiosugar complexes derived from glucose, lactose and galactose is reported. The reactions of 1,3-dibenzyl-4,5-diphenyl-imidazol-2-ylidene gold(I) chloride (NHC1-Au-Cl) with pre-synthesized glycosyl thiols under mildly basic conditions gave the desired NHC-Au-thiosugar complexes in high to excellent yields (79–91%). The complexes retain the strong and redox-active Au-S bond contained in Auranofin. All complexes showed good solubility in biological media and were tested against the NCI 60 cancer cell panel for cytotoxicity. The synthesized NHC1-Au derivatives showed good activity in the medium to low micromolar region, while complex 2 showed activity in the low micromolar to nanomolar region against the tested cell lines. To provide a theoretical structure of 4, computational calculations were carried out based on the crystal structures of NHC-Au-SCN and NHC-Au-S-C₆H₄OMe.     

pH-Controlled Supramolecular Self-Assembly of Naphthalenediimide Appended l-Alanine and Ethylenediamine Asymmetric Bolaamphiphile

Design, synthesis and characterization of novel (2S)-2-[7-(2-aminoethyl)-1,3,6,8-tetraoxo-3,6,7,8-tetrahydrobenzo[lmn][3,8]phenanthrolin-2(1H)-yl]propanoic acid ( 1 ) bolaamphiphile, which combine naphthalene diimide (NDI) appended with l -alanine at one end of imide and ethylenediamine at the other end. An l -alanine bearing NDI-based asymmetric bolaamphiphile self-assembled at various pH ranging from 2 to 10 forms a variety of supramolecular nanostructures. The UV-Vis and emission spectroscopic techniques employed for the optical and photophysical properties study of bolaamphiphile 1 at various pH values. It was revealed that the change in pH alters both the optical and photophysical properties of bolaamphiphile 1 . Theoretical calculations used to investigate the electronic properties of the bolaamphiphile 1 . Dynamic light scattering experiments displayed formation of aggregates in solution and scanning electron microscopy (SEM) was used to visualize the nanostructures formed on silicon wafers. Furthermore, the X-ray diffraction was used to determine the nanostructure's packing properties i. e. crystalline/amorphous. Experimental circular dichroism (CD) spectroscopy results inferred and revealed the induction of chirality into the supramolecular systems, which was shown to be pH dependent. This study clearly demonstrates the manipulation of pH can control/tune chiral supramolecular structures and provide future methods for the development of chiral recognition and catalysis study.     

Determination of gymnemagenin in rat plasma using high‐performance liquid chromatography–tandem mass spectrometry: application to pharmacokinetics after oral administration of Gymnema sylvestre extract

A sensitive and rapid high‐performance liquid chromatography–tandem mass spectrometry (HPLC‐MS/MS) method has been developed and validated for the determination of gymnemagenin (GMG), a triterpene sapogenin from Gymnema sylvestre, in rat plasma using withaferin A as the internal standard (IS). Plasma samples were simply extracted using liquid–liquid extraction with tetra‐butyl methyl ether. Chromatographic separation was performed on Luna C₁₈ column using gradient elution of water and methanol (with 0.1% formic acid and 0.3% ammonia) at a flow rate of 0.8 mL/min. GMG and IS were eluted at 4.64 and 4.36 min, ionized in negative and positive mode, respectively, and quantitatively estimated using multiple reaction monitoring (MRM) mode. Two MRM transitions were selected at m/z 505.70 → 455.5 and m/z 471.50 → 281.3 for GMG and IS, respectively. The assay was linear over the concentration range of 5.280–300.920 ng/mL. The mean plasma extraction recoveries for GMG and IS were found to be 80.92 ± 8.70 and 55.63 ± 0.76%, respectively. The method was successfully applied for the determination of pharmacokinetic parameters of GMG after oral administration of G. sylvestre extract. Copyright © 2012 John Wiley & Sons, Ltd.