Selective Determination of Pyridine Alkaloids in Tobacco by PFTBA Ions/Analyte Molecule Reaction Ionization Ion Trap Mass Spectrometry

The application of perfluorotributylamine (PFTBA) ions/analyte molecule reaction ionization for the selective determination of tobacco pyridine alkaloids by ion trap mass spectrometry (IT-MS) is reported. The main three PFTBA ions (CF3+, C3F5+, and C5F10N+) are generated in the external source and then introduced into ion trap for reaction with analytes. Because the existence of the tertiary nitrogen atom in the pyridine makes it possible for PFTBA ions to react smoothly with pyridine and forms adduct ions, pyridine alkaloids in tobacco were selectively ionized and formed quasi-molecular ion [M + H]+and adduct ions, including [M + 69]+, [M + 131]+, and [M + 264]+, in IT-MS. These ions had distinct abundances and were regarded as the diagnostic ions of each tobacco pyridine alkaloid for quantitative analysis in selected-ion monitoring mode. Results show that the limit of detection is 0.2 μg/mL, and the relative standard deviations for the seven alkaloids are in the range of 0.71% to 6.8%, and good recovery of 95.6% and 97.2%. The proposed method provides substantially greater selectivity and sensitivity compared with the conventional approach and offers an alternative approach for analysis of tobacco alkaloids

Online unicasting and multicasting in software-defined networks

Software-Defined Networking (SDN) has emerged as the paradigm of the next-generation networking through separating the control plane from the data plane. In a software-defined network, the forwarding table at each switch node usually is implemented by expensive and power-hungry Ternary Content Addressable Memory (TCAM) that only has limited numbers of entries. In addition, the bandwidth capacity at each link is limited as well. Provisioning quality services to users by admitting their requests subject to such critical network resource constraints is a fundamental problem, and very little attention has been paid. In this paper, we study online unicasting and multicasting in SDNs with an objective of maximizing the network throughput under network resource constraints, for which we first propose a novel cost model to accurately capture the usages of network resources at switch nodes and links. We then devise two online algorithms with competitive ratios O(log n) and O(Kϵlog n) for online unicasting and multicasting, respectively, where n is the network size, K is the maximum number of destinations in any multicast request, and ϵ is a constant with 0 < ϵ ≤ 1. We finally evaluate the proposed algorithms empirically through simulations. The simulation results demonstrate that the proposed algorithms are very promising

Studies on Gas-phase Cyclometalations of [ArNi(PPh3)n]+ (n = 1 or 2) by Electrospray Ionization Tandem Mass Spectrometry

Gas-phase cyclometalation of [ArNi(PPh3)n]+ (n = 1, 2) complexes have been studied by ESI-MS/MS. The electron-donating substituents of aromatic iodides in the para position were found to inhibit the cyclometalation process of losing ArH, while the electron-withdrawing substituents in the para position were found to enhance it. These results indicate that the cyclometalation process of losing ArH is favored by electron-deficient aromatic groups. In addition, the detailed dissociation pathways of the cationic nickel complexes were studied, and among these pathways, the process of aryl-aryl interchange was also found to proceed in ESI-MS/MS

Monitoring Enzyme Reaction and Screening of Inhibitors of Acetylcholinesterase by Quantitative Matrix-Assisted Laser Desorption/Ionization Fourier Transform Mass Spectrometry

A matrix-assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS)–based assay was developed for kinetic measurements and inhibitor screening of acetylcholinesterase. Here, FTMS coupled to MALDI was applied to quantitative analysis of choline using the ratio of choline/acetylcholine without the use of additional internal standard, which simplified the experiment. The Michaelis constant (Km) of acetylcholinesterase (AChE) was determined to be 73.9 μmol L−1 by this approach. For Huperzine A, the linear mixed inhibition of AChE reflected the presence of competitive and noncompetitive components. The half maximal inhibitory concentration (IC50) value of galantamine obtained for AChE was 2.39 μmol L−1. Inhibitory potentials of Rhizoma Coptidis extracts were identified with the present method. In light of the results the referred extracts as a whole showed inhibitory action against AChE. The use of high-resolution FTMS largely eliminated the interference with the determination of ACh and Ch, produced by the low-mass compounds of chemical libraries for inhibitor screening. The excellent correlation with the reported kinetic parameters confirms that the MS-based assay is both accurate and precise for determining kinetic constants and for identifying enzyme inhibitors. The obvious advantages were demonstrated for quantitative analysis and also high-throughput characterization. This study offers a perspective into the utility of MALDI-FTMS as an alternate quantitative tool for inhibitor screening of AChE

Ex Situ Reconstruction-Shaped Ir/CoO/Perovskite Heterojunction for Boosted Water Oxidation Reaction

The oxygen evolution reaction (OER) is the performance-limiting step in the process of water splitting. In situ electrochemical conditioning could induce surface reconstruction of various OER electrocatalysts, forming reactive sites dynamically but at the expense of fast cation leaching. Therefore, achieving simultaneous improvement in catalytic activity and stability remains a significant challenge. Herein, we used a scalable cation deficiency-driven exsolution approach to ex situ reconstruct a homogeneous-doped cobaltate precursor into an Ir/CoO/perovskite heterojunction (SCI-350), which served as an active and stable OER electrode. The SCI-350 catalyst exhibited a low overpotential of 240 mV at 10 mA cm-2 in 1 M KOH and superior durability in practical electrolysis for over 150 h. The outstanding activity is preliminarily attributed to the exponentially enlarged electrochemical surface area for charge accumulation, increasing from 3.3 to 175.5 mF cm-2. Moreover, density functional theory calculations combined with advanced spectroscopy and 18O isotope-labeling experiments evidenced the tripled oxygen exchange kinetics, strengthened metal-oxygen hybridization, and engaged lattice oxygen oxidation for O-O coupling on SCI-350. This work presents a promising and feasible strategy for constructing highly active oxide OER electrocatalysts without sacrificing durability

The oyster genome reveals stress adaptation and complexity of shell formation

The Pacific oyster Crassostrea gigas belongs to one of the most species-rich but genomically poorly explored phyla, the Mollusca. Here we report the sequencing and assembly of the oyster genome using short reads and a fosmid-pooling strategy, along with transcriptomes of development and stress response and the proteome of the shell. The oyster genome is highly polymorphic and rich in repetitive sequences, with some transposable elements still actively shaping variation. Transcriptome studies reveal an extensive set of genes responding to environmental stress. The expansion of genes coding for heat shock protein 70 and inhibitors of apoptosis is probably central to the oyster's adaptation to sessile life in the highly stressful intertidal zone. Our analyses also show that shell formation in molluscs is more complex than currently understood and involves extensive participation of cells and their exosomes. The oyster genome sequence fills a void in our understanding of the Lophotrochozoa. © 2012 Macmillan Publishers Limited. All rights reserved

EFEMP1 in Direct Inguinal Hernia: correlation with TIMP3 and Regulation Toward Elastin Homoeostasis as Well as Fibroblast Mobility

Aim This basic research aimed to detect the inner-correlation of EGF containing fibulin extracellular matrix protein 1 (EFEMP1), TIMP metallopeptidase inhibitor 3 (TIMP3), matrix metalloprotease 9 (MMP9), elastin (ELN) in direct inguinal hernia (IH), and their effect on fibroblasts motility. Methods Transversalis fascia samples from 20 direct IH patients and 20 varicocele (served as controls) patients were collected for detecting EFEMP1, TIMP3, MMP9 and ELN expressions by immunohistochemistry assay. Fibroblasts L929 cells were transfected with EFEMP1 overexpression plasmid or knock-down plasmid to investigate the influence of EFEMP1 dysregulation on L929 cell migration, invasion, TIMP3, MMP9 and ELN expressions. Additionally, rescue experiments were performed by adding TIMP3 knockdown plasmid to the EFEMP1-overexpressed L929 cells. Results Transversalis fascia EFEMP1, TIMP3 and ELN expressions were decreased, but MMP9 expression was increased in IH patients compared with controls. In IH patients, EFEMP1 was not correlated with TIMP3, but positively correlated with ELN and negatively correlated with MMP9; TIMP3 negatively correlated with MMP9, but positively correlated with ELN. Overexpression of EFEMP1 did not affect TIMP3 expression but increased ELN expression and decreased MMP9 expression in L929 cells. In addition, EFEMP1 suppressed L929 cell migration and invasion. The following rescue experiments indicated that silencing TIMP3 attenuated the effect of EFEMP1 overexpression on MMP9 and ELN expressions as well as the effect of EFEMP1 overexpression on cell migration and invasion in L929 cells. Conclusions EFEMP1 is downregulated in direct IH, and it regulates ELN homoeostasis as well as fibroblast mobility via interacting with TIMP3

A Bio-Inspired Polarization Sensor with High Outdoor Accuracy and Central-Symmetry Calibration Method with Integrating Sphere

A bio-inspired polarization sensor with lenses for navigation was evaluated in this study. Two new calibration methods are introduced, referred to as &ldquo;central-symmetry calibration&rdquo; (with an integrating sphere) and &ldquo;noncontinuous calibration&rdquo;. A comparison between the indoor calibration results obtained from different calibration methods shows that the two proposed calibration methods are more effective. The central-symmetry calibration method optimized the nonconstant calibration voltage deviations, caused by the off-axis feature of the integrating sphere, to be constant values which can be calibrated easily. The section algorithm proposed previously showed no experimental advantages until the central-symmetry calibration method was proposed. The outdoor experimental results indicated that the indoor calibration parameters did not perform very well in practice outdoor conditions. To establish the reason, four types of calibration parameters were analyzed using the replacement method. It can be concluded that three types can be easily calibrated or affect the sensor accuracy slightly. However, before the sensor is used outdoors every time, the last type must be replaced with the corresponding outdoor parameter, and the calculation needs a precise rotary table. This parameter, which is mainly affected by the spectrum of incident light, is the main factor determining the sensor accuracy. After calibration, the sensor reaches an indoor accuracy of &plusmn;0.009&deg; and a static outdoor accuracy of &plusmn;0.05&deg; under clear sky conditions. The dynamic outdoor experiment shows a &plusmn;0.5&deg; heading deviation between the polarization sensor and the inertial navigation system with a &plusmn;0.06&deg; angular accuracy

IntroVNMT: An Introspective Model for Variational Neural Machine Translation

We propose a novel introspective model for variational neural machine translation (IntroVNMT) in this paper, inspired by the recent successful application of introspective variational autoencoder (IntroVAE) in high quality image synthesis. Different from the vanilla variational NMT model, IntroVNMT is capable of improving itself introspectively by evaluating the quality of the generated target sentences according to the high-level latent variables of the real and generated target sentences. As a consequence of introspective training, the proposed model is able to discriminate between the generated and real sentences of the target language via the latent variables generated by the encoder of the model. In this way, IntroVNMT is able to generate more realistic target sentences in practice. In the meantime, IntroVNMT inherits the advantages of the variational autoencoders (VAEs), and the model training process is more stable than the generative adversarial network (GAN) based models. Experimental results on different translation tasks demonstrate that the proposed model can achieve significant improvements over the vanilla variational NMT model