Surface swabbing technique for the rapid screening for pesticides using ambient pressure desorption ionization with high-resolution mass spectrometry

A rapid screening method for pesticides has been developed to promote more efficient processing of produce entering the United States. Foam swabs were used to recover a multiclass mixture of 132 pesticides from the surfaces of grapes, apples, and oranges. The swabs were analyzed using direct analysis in real time (DART) ionization coupled with a high‐resolution Exactive Orbitrap? mass spectrometer. By using a DART helium temperature gradient from 100–350°C over 3 min, a minimal separation of analytes based on volatility differences was achieved. This, combined with the Exactive's mass resolution of 100 000, allowed the chromatographic step, along with the typical compositing and extraction steps associated with gas chromatography/mass spectrometry (GC/MS) or liquid chromatography/mass spectrometry (LC/MS) approaches, to be eliminated. Detection of 86% of the analytes present was consistently achieved at levels of 2 ng/g (per each apple or orange) and 10 ng/g (per grape). A resolution study was conducted with four pairs of isobaric compounds analyzed at a mass resolution of 100 000. Baseline separation was achieved with analyte ions differing in mass by 25 ppm and analyte ions with a mass difference of 10 ppm were partially resolved. In addition, field samples that had undergone traditional sample preparation using QuEChERS (quick, easy, cheap, rugged, and safe) were analyzed using both LC/MS and DART‐MS and the results from the two techniques were found to be comparable in terms of identification of the pesticides present. The use of swabs greatly increased sample throughput by reducing sample preparation and analysis time. Published in 2010 by John Wiley & Sons, Ltd.     

In vitro anti-HMPV activity of meroditerpenoids from marine alga Stypopodium zonale (Dictyotales)

In this paper, we evaluated the antiviral activity against HMPV replication of crude extract of the marine algae Stypopodium zonale and of two meroditerpenoids obtained from it, atomaric acid and epitaondiol, and a methyl ester derivative of atomaric acid. Their selectivity indexes were 20.78, >56.81, 49.26 and 12.82, respectively. Compared to ribavirin, the substances showed a relatively low cytotoxicity on LLC-MK2 cells, with a significant antiviral activity, inhibiting at least 90% of viral replication in vitro, which demonstrates the potential of these marine natural products to combat infections caused by HMPV in vitro.     

Enantioselective organocatalytic Michael-hemiketalization catalyzed by a trans-bifunctional indane thiourea catalyst

An efficient, convenient and enantioselective Michael-hemiketalization reaction has been developed for the synthesis of naphthoquinones. In this work, a novel trans-bifunctional indane thiourea catalyst has been reported to promote this process to afford high yields (up to 99%) and high to excellent enantiomeric excesses (90-98% ee).     

Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere via N-H imines as an intramolecular directing group

Copper-catalyzed benzylic C-H oxygenation under an oxygen atmosphere was developed starting from carbonitriles and Grignard reagents via N-H imine intermediates. The present process is characterized by the following two-step sequence in a one-pot manner: (1) addition of Grignard reagents to carbonitriles to form N-H imines and (2) benzylic C-H oxygenation (C═O bond formation) triggered by 1,5-hydrogen atom transfer with transient iminyl copper species.     

On the roles of solid-bound ligand scavengers in the removal of palladium residues and in the distinction between homogeneous and heterogeneous catalysis

We have studied the roles and behavior of typical resin- and silica-bound thiol scavengers in the removal of palladium (Pd) residues and in the determination of the true catalytic species in the Heck coupling of bromobenzene and styrene. The results of Pd scavenging and catalyst poisoning by elemental analysis (EA) and transmission electron microscopy (TEM) indicate that silica-bound thiols have an advantage over resin-bound thiols in residual Pd removal from a Heck reaction solution and that all of these scavengers poison effectively the catalytic species but hardly scavenge Pd clusters, even as small as 1 nm from solution presumably because of the steric barrier. Because of a smaller proportion of soluble Pd clusters, using a molecular Pd precatalyst results in a much higher Pd scavenging efficiency than using a supported Pd particle precatalyst. With the aid of catalyst poisoning by the scavengers, filtration testing and TEM studies further illustrate that Pd clusters are inactive for the Heck reaction over Pd(0)/SiO(2), with molecular Pd(0) being solely active. Studies through EA and thermogravimetric analysis suggest that the bound thiols are leached from the scavengers to a different extent at reaction temperatures of 90-135 °C, probably owing to base-catalyzed decomposition or based-promoted dissociation of functional groups from the surfaces, leading to interaction between leached thiols and a solid Pd precatalyst. Meanwhile, the effect of solid-bound thiol binding to soluble Pd on the efficiency of Pd scavenging and the impact of a scavenger on the Pd leaching from supported Pd particles are discussed.     

Design and performance analysis of MAC schemes for Wireless Sensor Networks Powered by Ambient Energy Harvesting

Energy consumption is a perennial issue in the design of wireless sensor networks (WSNs) which typically rely on portable sources like batteries for power. Recent advances in ambient energy harvesting technology have made it a potential and promising alternative source of energy for powering WSNs. By using energy harvesters with supercapacitors, WSNs are able to operate perpetually until hardware failure and in places where batteries are hard or impossible to replace. In this paper, we study the performance of different medium access control (MAC) schemes based on CSMA and polling techniques for WSNs which are solely powered by ambient energy harvesting using energy harvesters. We base the study on (i) network throughput (S), which is the rate of sensor data received by the sink, (ii) fairness index (F), which determines whether the bandwidth is allocated to each sensor node equally and (iii) inter-arrival time (γ) which measures the average time difference between two packets from a source node. For CSMA, we compare both the slotted and unslotted variants. For polling, we first consider identity polling. Then we design a probabilistic polling protocol that takes into account the unpredictability of the energy harvesting process to achieve good performance. Finally, we present an optimal polling MAC protocol to determine the theoretical maximum performance. We validate the analytical models using extensive simulations incorporating experimental results from the characterization of different types of energy harvesters. The performance results show that probabilistic polling achieves high throughput and fairness as well as low inter-arrival times.     

非辐射边馈电的宽带双层微带贴片天线

介绍了一种非辐射边馈电的宽带双层微带贴片天线单元,并对其参数特性进行了仿真研究,结果表明,通过在寄生贴片上开3～5个与极化方向相平行的缝,可有效抑制天线的交叉极化,同时改善天线的阻抗带宽。相比传统双层微带贴片,该天线单元的阻抗带宽可提高3%以上,而交叉极化指标相当。当该单元应用于阵列天线设计时,可简化馈电网络,便于实现宽带、高效、大扫描角的微带共面馈电天线阵。对X波段8×8单元实验小阵的测试结果表明,该天线在17.6%的频段内具有良好的交叉极化性能及较高的工作效率。     

Accurate frequency response characterization of photoreceivers

An accurate frequency response characterization method for photoreceivers with optical heterodyne technique is presented in this paper.The characterization is implemented with two single-mode tunable lasers operating near the wavelength of 1.55 μm.The errors introduced by extra fixtures as well as laser output fluctuations are considered and calibrated simultaneously.Compared with previous works,the proposed calibration procedures are more complete.Experimental results indicate that the signific...     

Synthesis of fullerene@gold core-shell nanostructures

A "direct encapsulation" method was developed for the synthesis of highly stable water-soluble fullerene@gold core-shell nanostructures, with gold nanoshells showing either closed or porous morphology. This gold nano-shell coating formed a "nano-oven", capable of decomposing encapsulated fullerene molecules rapidly when irradiated by laser. We envisaged this being a useful tool for chemical reactions as well as a novel scaffold for nano-material synthesis.     

Occurrence and estimation of trans-resveratrol in one-year-old canes from seven major Chinese grape producing regions

The concentration of trans-resveratrol in 165 grape cane samples from three major grape production regions and four large distribution centers of Chinese wild Vitis species were determined by reversed-phase high-performance liquid chromatography (HPLC). Among the different genotype groups and purpose of uses, cultivars of V. vinifera had much higher amounts of trans-resveratrol than did the cultivars of both V. labrusca or V. labrusca and V. vinifera hybrids, and within the V. vinifera species, significantly higher amounts of trans-resveratrol were found in wine grapes compared to table ones. No significant differences were observed between V. labrusca and its hybrids from crosses with V. vinifera, and between red cultivars and white ones (P < 0.05 or P < 0.01). The contents of trans-resveratrol, as a normal constituent occurring in grape canes, in Chinese wild species of V. amurensis, V. pentagona, and V. davidii from their native habitats were also relatively high.