Simultaneous discrimination of jasmonic acid stereoisomers by CE-QTOF-MS employing the partial filling technique

Jasmonic acid (JA), an essential plant hormone controlling the plant defense signaling system and developmental processes, has stereospecific bioactivities that have not been well understood mainly due to the limitation in separation and detection methodologies. In this work, a fast CE-UV method based on short-end injection technique and a sensitive CE-QTOF-MS method based on partial filling technique were successfully developed for the enantioseparation of racemic JA. The successive coating technique was also involved by modifying the capillary with multiple ionic polymer layers of polybrene-dextran sulfate-polybrene. This was the first report on the direct resolution of both pairs of JA enantiomers, including two naturally occurring JA stereoisomers. Although no pure JA stereoisomers were commercially available, all the separated JA stereoisomers were identified indirectly by comparing the difference between the racemic standard and plant samples based on the presence and the ratio of each stereoisomer. Satisfactory results were obtained in terms of sensitivity (LOD, 24 ng/mL or 0.7 fmol for single JA stereoisomer) using 45 mmol/L ammonium acetate at pH 4.5 containing 70 mmol/L α-CD as the buffer system. This established CE-QTOF-MS method was later successfully applied for the study of the naturally occurring JA stereoisomers in wounded tobacco leaves.     

MMI Double-Wavelength Optical Power Splitter

An MMI double-wavelength optical power splitter for both 1.55μm and 1.3μm is presented in this paper. Analysis shows that it can divide power equally for both 1.55μm and 1.3μm.     

光子晶体缺陷模的带宽与品质因子研究

利用光学传输矩阵法研究了结构参量对缺陷态光子晶体的缺陷模带宽和品质因子的影响.研究发现,当缺陷介质层厚度h₀的值较小时,缺陷模的带宽很小且基本保持不变;当h₀较大时,缺陷模的带宽随h₀的增加而快速增加.另外发现,缺陷模的品质因子在某个h₀处取最大值.但是总体上看,h₀较小时的品质因子要远大于h₀较大时的品质因子.此外,缺陷模的品质因子随光子晶体的周期数增加而急剧增加约4.788倍,而带宽则随周期数的增加而急剧减少约4.788倍.当周期数为13时就可以获得10⁹以上的品质因子值和小于10^-9的相对带宽值.     

Two-dimensional overlapping-image multimode interference couplers

The overlapping-imaging effect of one-dimensional (1D) multimode interference (MMI) coupler is widened to study the two-dimensional (2D) MMI coupler. 2D overlapping-image MMI couplers permit uniform and nonuniform 2D power splitting. Analytical formulas are derived for the intensities and phases of the overlapping-images at the end of MMI section. The overlapping-imaging properties in 2D MMI couplers are also concluded. And the guided-mode propagation analysis method is used to confirm the analytical results.     

Identification of hydroxyl radical oxidation products of N‐hexanoyl‐homoserine lactone by reversed‐phase high‐performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry

A reversed‐phase high‐performance liquid chromatography/electrospray tandem mass spectrometry method was developed for the characterization of hydroxyl radical oxidation products of N‐hexanoyl‐homoserine lactone (C6‐HSL), a member of the N‐acylhomoserine lactone (AHL) class of microbial quorum‐sensing signaling molecules identified in many Gram‐negative strains of bacteria. Six products were identified: four with molecular weight (MW) of 213 and two with MW of 260. The characteristic product ions formed through collision‐induced dissociation (CID) provided diagnostic structural information. One of the photolysis products was determined to be N‐(3‐oxohexanoyl)homoserine lactone (3OC6‐HSL), a highly active quorum‐sensing signal, by comparison with a reference standard. Three structural isomers with the same mass as 3OC6‐HSL were identified as acyl side chain oxidized C6‐HSL (keto/enol functionalized) by accurate mass measurement and the structures of these products were proposed from CID spectral interpretation. Two structural isomers formed from concurrent oxidation and nitration of C6‐HSL were also observed and their structures were postulated based on CID spectra. In addition to the six hydroxyl radical oxidation products formed from the C6‐HSL precursor, five additional compounds generated from combined oxidation and lactonolysis of C6‐HSL were identified and structures were postulated. Copyright © 2009 John Wiley & Sons, Ltd.     

Development and validation of a sensitive LC‐MS/MS‐ESI method for the determination of ivabradine in human plasma: application to a pharmacokinetic study

A sensitive, rapid assay method for estimating ivabradine in human plasma has been developed and validated using liquid chromatography coupled to tandem mass spectrometry with electrospray ionization in the positive‐ion mode. The procedure involved extraction of ivabradine and the internal standard (IS) from human plasma by solid‐phase extraction. Chromatographic separation was achieved using an isocratic mobile phase (0.1% formic acid–methanol, 60:40, v/v) at a flow rate of 1.0 mL/min on an Aglient Eclipse XDB C₈ column (150 × 4.6 mm, 5 µm; maintained at 35°C) with a total run time of 4.5 min. Detection was achieved using an Applied Biosystems MDS Sciex (Concord, Ontario, Canada) API 3200 triple‐quadrupole mass spectrometer. The MS/MS ion transitions monitored were 469–177 for ivabradine and 453–177 for IS. Method validation was performed according to Food and Drug Administration guidelines, and the results met the acceptance criteria. The calibration curve was linear over a concentration range of 0.1–200 ng/mL. The lower limit of quantitation achieved was 0.1 ng/mL. Intra‐ and inter‐day precisions were in the range of 1.23–14.17% and 5.26‐8.96%, respectively. Finally, the method was successfully used in a pharmacokinetic study that measured ivabradine levels in healthy volunteers after a single 5 mg oral dose of ivabradine. Copyright © 2013 John Wiley & Sons, Ltd.     

Molecular-level examination of Cu2+ binding structure for amyloid fibrils of 40-residue Alzheimer's β by solid-state NMR spectroscopy

Cu(2+) binding to Alzheimer's β (Aβ) peptides in amyloid fibrils has attracted broad attention, as it was shown that Cu ion concentration elevates in Alzheimer's senile plaque and such association of Aβ with Cu(2+) triggers the production of neurotoxic reactive oxygen species (ROS) such as H(2)O(2). However, detailed binding sites and binding structures of Cu(2+) to Aβ are still largely unknown for Aβ fibrils or other aggregates of Aβ. In this work, we examined molecular details of Cu(2+) binding to amyloid fibrils by detecting paramagnetic signal quenching in 1D and 2D high-resolution (13)C solid-state NMR (SSNMR) for full-length 40-residue Aβ(1-40). Selective quenching observed in (13)C SSNMR of Cu(2+)-bound Aβ(1-40) suggested that primary Cu(2+) binding sites in Aβ(1-40) fibrils include N(ε) in His-13 and His-14 and carboxyl groups in Val-40 as well as in Glu sidechains (Glu-3, Glu-11, and/or Glu-22). (13)C chemical shift analysis demonstrated no major structural changes upon Cu(2+) binding in the hydrophobic core regions (residues 18-25 and 30-36). Although the ROS production via oxidization of Met-35 in the presence of Cu(2+) has been long suspected, our SSNMR analysis of (13)C(ε)H(3)-S- in M35 showed little changes after Cu(2+) binding, excluding the possibility of Met-35 oxidization by Cu(2+) alone. Preliminary molecular dynamics (MD) simulations on Cu(2+)-Aβ complex in amyloid fibrils confirmed binding sites suggested by the SSNMR results and the stabilities of such bindings. The MD simulations also indicate the coexistence of a variety of Cu(2+)-binding modes unique in Aβ fibril, which are realized by both intra- and intermolecular contacts and highly concentrated coordination sites due to the in-register parallel β-sheet arrangements.     

Supercritical fluid extraction of sinomenine from Sinomenium acutum (Thumb) Rehd et Wils

Supercritical carbon dioxide, with and without a methanol modifier, was used to extract sinomenine from Sinomenium acutum (Thumb) Rehd et Wils. Sinomenine determinations were carried out using high-performance liquid chromatography (HPLC). The results show that the yield obtained after 2.5 h extraction with methanol-modified supercritical carbon dioxide was the highest (7.47 mg/g), while that obtained with only supercritical carbon dioxide was the lowest (0.17 mg/g). The recovery obtained with supercritical carbon dioxide, with and without a methanol modifier, could not be increased greatly by the method of the alkalinization of sample. Higher recoveries were obtained than extraction using methanol in Soxhlet extractor.