Rapid separation and identification of major constituents in Pseudolarix kaempferi by ultra‐performance liquid chromatography coupled with electrospray and quadrupole time‐of‐flight tandem mass spectrometry

A rapid and reliable method based on ultra‐performance liquid chromatography (UPLC) coupled with photodiode‐array detection (PDA) and electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry (ESI‐Q‐TOF‐MS/MS) has been developed for separation and identification of major constituents in extracts of root bark of Pseudolarix kaempferi Gordon (PKG). Identification of the constituents was carried out by interpretation of their retention times, UV absorption spectra, MS and MS/MS spectra, as well as the data provided by authentic standards and literatures. A total of 20 components were separated in only 8.0 min on a small particle size C₁₈ column (1.7 µm). These components included nine diterpene acids, seven glycosides and four triterpenoids, among which pseudolaric acid C‐O‐β‐D‐glucopyranoside and pseudolaric acid C₂‐O‐β‐D‐glucopyranoside were separated and identified for the first time in this study. Furthermore, the fragmentation patterns of the three types of compounds were elucidated for the first time. This established UPLC‐PDA/Q‐TOF‐MS/MS method is reliable and effective for the separation and identification of the 20 compounds and will be useful for quality control of the crude materials of Pseudolarix kaempferi Gordon and their related preparations. Copyright © 2009 John Wiley & Sons, Ltd.     

基于特殊混料模型D-最优设计搜索的交换点式门限接受算法

在搜索混料模型D-最优设计的计算机算法领域,主流算法包括经典的Fedorov算法,以及元启发类算法,但两者在一些特定的优化问题上,分别在收敛速度和收敛精度方面有进一步提升的空间.文章分别探讨了可能造成这种情况的两类算法各自的局限性,并采取优势互补的策略,构建了交换点式门限接受算法,即ETA (exchange threshold accepting)算法.以含倒数项混料模型为例,文章验证了ETA算法生成设计的D-最优性,并分别与Fedorov算法和元启发类的ProjPSO算法作比较.结果表明,至少在某些特殊的混料模型D-最优设计的搜索方面,ETA算法在收敛速度和精度方面均具有一定的优势.     

不确定度优于0.035%的绝对光谱响应率标准探测器

讨论了由无窗硅光电二极管构成的反射式陷阱探测器的设计方案和工作原理 ,通过实验测试证明它具有良好的线性、空间响应均匀性、偏振非敏感性和稳定性。在可见波段的7个激光波长上（488nm-786nm),通过低温辐射计标定了陷阱探测器的绝对光谱响应率,不确定度小于0.035%,比现有的标准辐射源的精度提高了约2个量级,证明其可以作为高精度的绝对光谱响应率标准探测器。     

Poly(γ‐benzyl‐L‐glutamate)‐functionalized single‐walled carbon nanotubes from surface‐initiated ring‐opening polymerizations of N‐carboxylanhydride

Single‐walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ‐benzyl‐L ‐glutamate) (PBLG) by ring‐opening polymerizations of γ‐benzyl‐L ‐glutamic acid‐based N‐carboxylanhydrides (NCA‐BLG) using amino‐functionalized SWCNTs (SWCNT‐NH₂) as initiators. The SWCNT functionalization has been verified by FTIR spectroscopy and transmission electron microscopy. The FTIR study reveals that surface‐attached PBLGs adopt random‐coil conformations in contrast to the physically absorbed or bulk PBLGs, which exhibit α‐helical conformations. Raman spectroscopic analysis reveals a significant alteration of the electronic structure of SWCNTs as a result of PBLG functionalization. The PBLG‐functionalized SWCNTs (SWCNT‐PBLG) exhibit enhanced solubility in DMF. Stable DMF solutions of SWCNT‐PBLG/PBLG with a maximum SWCNTs concentration of 259 mg L^?1 can be readily obtained. SWCNT‐PBLG/PBLG solid composites have been characterized by differential scanning calorimetry, thermogravimetric analysis, wide/small‐angle X‐ray scattering (W/SAXS), scanning electron microscopy, and polarized optical microscopy for their thermal or morphological properties. Microfibers containing SWCNT‐PBLG and PBLG can also be prepared via electrospinning. WAXS characterization reveals that SWCNTs are evenly distributed among PBLG rods in solution and in the solid state where PBLGs form a short‐range nematic phase interspersed with amorphous domains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2340–2350, 2010     

Enrichment and isolation of barbigerone from Millettia pachycarpa Benth. using high‐speed counter‐current chromatography and preparative HPLC

Enrichment of the anti‐tumor compound barbigerone along with a rotenoid derivative from Millettia pachycarpa Benth. was performed by a two‐step high‐speed counter‐current chromatography (HSCCC) separation process. In the first step, 155.8 mg of target fraction (Fra6) was obtained from 400 mg ethyl acetate extract of M. pachycarpa Benth. with an increase in barbigerone from 5.1 to 13% via HSCCC using a solvent system of n‐hexane–ethyl acetate–methanol–water (5:4:5:3, v/v) under normal phase head to tail elution. HSCCC was repeated to eliminate the major contaminant in this initial fraction 6. After a separation time of 65 min, 22.1 mg barbigerone of 87.7% purity was obtained from Fra6 with the ternary solvent system of n‐hexane–methanol–water (2:2:1, v/v) under normal phase elution. Finally, preparative HPLC was employed for the further isolation of barbigerone and the rotenoid derivative. The structures were confirmed by ESI‐MS, ¹H NMR and ¹³C NMR.     

Separation of anthraquinone compounds from the seed of Cassia obtusifolia L. using recycling counter‐current chromatography

Recycling counter‐current chromatography (CCC) together with step‐gradient CCC and medium‐pressure liquid chromatography (MPLC) was employed to separate nine anthraquinone compounds from Cassia obtusifolia L. in this study. The results showed that recycling CCC is a powerful tool for compounds that are difficult to separate with common elution mode. CCC was the better option for crude material while MPLC had advantage for the final tuning. The combination of recycling CCC and MPLC could simplify the method exploring process in the separation process. The structures of these compounds were identified according to their mass spectra, by ¹H‐NMR and compared with standard compounds.     

Water‐Soluble Thermoresponsive α‐Helical Polypeptide with an Upper Critical Solution Temperature: Synthesis,Characterization, and Thermoresponsive Phase Transition Behaviors

Water‐soluble polypeptides bearing 1‐alkylimidazolium (methyl or n‐butyl) and various counter‐anions (i.e., Cl⁻, I⁻ or BF₄⁻) are prepared by ring‐opening polymerization of γ‐4‐chloromethylbenzyl‐_l‐glutamate‐based N‐carboxyanhydride ( 3 ), post‐polymerization of poly(γ‐4‐chloromethylbenzyl‐_l‐glutamate) ( 4 ), and ion‐exchange reaction. Circular dichroism (CD) analysis reveals that the resulting polypeptides adopt an α‐helical conformation in water with a fractional helicity in the range of 30%–56% at 20 °C and exhibit good conformational stability against temperature variations. The polypeptides exhibit lower critical solution temperature (LCST)‐type or upper critical solution temperature (UCST)‐type transitions in organic solvents or in water. The UCST‐type transition temperature (T_pt) in water is independent on the molecular weight, yet it decreases upon addition of NaCl and increases upon addition of NaI or NaBF₄, suggesting a mainly electrostatic interaction mechanism.

     

Elution-extrusion counter-current chromatography separation of five bioactive compounds from Dendrobium chrysototxum Lindl

The elution-extrusion counter-current chromatography (EECCC) method was firstly developed by Berthod in 2003 and has been used in natural products separation in recent years. The advantages of this method have been well documented such as reducing the separation time and solvent consumption. In the EECCC method, the time point of the extrusion step is very important during the whole separation process as it directly affects the resolutions, separation time and solvent consumption. However, how to choose a suitable time point to perform the extrusion step without decreasing the resolution has not been studied yet. In the present study, a strategy for systematically calculating the time point for extrusion was developed in theory and five bioactive compounds from the extract of Dendrobium chrysototxum Lindl. were separated and compared using normal CCC and EECCC method. Our results demonstrated that the accurate time point to perform the extrusion could be calculated and reduced both separation time and solvent consumption without losing separation performance. Using this EECCC method, five bioactive compounds were separated and purified with high purity. The separation time and solvent consumption were decreased from 200 min to 100 min and 5-2.5L during the separation process while the resolutions were still acceptable. Finally, 63 mg, 48 mg, 97 mg, 162 mg and 43 mg of hydroxyl phenanthrenes and bibenzyls with the purity of 98.7%, 98.0%, 98.2%, 99.0% and 98.7%, respectively were isolated from 1.2 g crude extract of D. chrysototxum Lindl. initially purified by column chromatography in one step separation. The purities of compounds were determined by HPLC. Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and NMR.     

Electron inducing soft errors in 28 nm system-on-Chip

ABSTRACT

The 28?nm system-on-chip (SoC) was irradiated by 12?MeV electron at the China Institute of Atomic Energy (CIAE) for the first time. Soft errors in the on-chip memory (OCM), D-Cache, Register and BRAM blocks were investigated. The obtained device cross sections are almost in the range of 10^?13 cm² to 10^?11 cm² for the blocks. The results demonstrate that electron fluence per pulse and the corresponding prompt dose rates have no influence on the soft errors in 28?nm SoC. The discrepancy was analyzed between proton and electron inducing soft errors in D-Cache and BRAM blocks, too. The secondary electron is considered as the dominant reason for soft errors caused by 12?MeV electron in 28?nm SoC.