The effect of cation size (H+, Li+, Na+, and K+) on McLafferty-type rearrangement of even-electron ions in mass spectrometry

Protonation and alkali-metal cation adduction are the most important ionization processes in soft-ionization mass spectrometry.Studies on the fragmentation mechanism of protonated and alkali-metal-cationized compounds in tandem mass spectrometry are essential and helpful for structural analysis.In some cases,it was often observed that a compound attached by different alkali-metal cations(or proton)exhibits similar fragmentation patterns but the relative abundances of product ions are different.This difference was considered to derive from the different electrostatic interactions of alkali-metal cations(or the bonded effect of proton)with the analyte.The alkali-metal cation with a smaller ionic radius shows stronger electrostatic interaction with the molecule because of its higher charge density.In addition,the bonded effect of the proton is stronger than the electrostatic interaction of the alkali-metal cation.In the present study,which used McLafferty-type rearrangements of even-electron ions([M+Cat]+,Cat=H,Li,Na,K)as model reactions,the effect of cation size in mass spectrometric fragmentation reactions is highlighted.These considerations were also successfully applied to interpret the similar but distinct fragmentation behavior of proton and alkali-metal cation adducts of a synthetic compound(2-(acetamido(phenyl)methyl)-3-oxobutanoate)and a drug(entecavir).     

Cu Doping-Induced Transformation from [Ag62S12(SBut)32]2+ to [Ag62−xCuxS12(SBut)32]4+ Nanocluster

The change in the valence state of nanocluster can induce remarkable changes in the properties and structure. However, achieving the valence state changes in nanoclusters is still a challenge. In this work, we use Cu²⁺ as dopant to “oxidize” [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ (4 free electrons) to obtain the new nanocluster: [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ with 2 free electrons. As revealed by its structure, the [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ (x=10∼21) has a similar structure to that of [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ precursor and all the Cu atoms occupy the surface site of nanocluster. It′s worth noting that with the Cu atoms doping, the [Ag_62−xCu_xS₁₂(SBu^t)₃₂]⁴⁺ nanocluster is more stable than [Ag₆₂S₁₂(SBu^t)₃₂]²⁺ at higher temperature and in electrochemical cycle. This result has laid a foundation for the subsequent application and exploration. Overall, this work reveals crystals structure of a new Ag−Cu nanocluster and offers a new insight into the electron reduction/oxidation of nanocluster.     

Scaling properties of azimuthal anisotropy in Au+Au and Cu+Cu Collisions at sqrt[s NN]=200 GeV

Differential measurements of elliptic flow (v2) for Au+Au and Cu+Cu collisions at sqrt[sNN]=200 GeV are used to test and validate predictions from perfect fluid hydrodynamics for scaling of v2 with eccentricity, system size, and transverse kinetic energy (KE T). For KE T identical with mT-m up to approximately 1 GeV the scaling is compatible with hydrodynamic expansion of a thermalized fluid. For large values of KE T mesons and baryons scale separately. Quark number scaling reveals a universal scaling of v2 for both mesons and baryons over the full KE T range for Au+Au. For Au+Au and Cu+Cu the scaling is more pronounced in terms of KE T, rather than transverse momentum.     

A realization of digital wireless transmission for MRI signals based on 802.11b

In this paper, a digital wireless transmission system based on 802.11b standard for magnetic resonance imaging (MRI) application is designed and built for the first time to eliminate the interference aroused by coil array cables. The analysis shows that the wireless receiver has a very high sensitivity to detect MRI signals. The modulation technique of differential quadrature phase shift keyed (DQPSK) can be applied to MRI data transmission with rate of 2 Mbps and bandwidth of 2 MHz. The bench test verifies that this wireless link has a dynamic range over 86 dB supporting up to 3 T MRI system data transmission. The 2D spin echo imaging of phantom is performed and the SNR of the image obtained by the wireless transmission can be comparable with that got by the coaxial cables.     

Self-assembled lamellar nanochannels in polyoxometalate-polymer nanocomposites for proton conduction

The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials,as it can enhance ion conductivity by offering short ion-transport pathways.In this work,we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels,by the electrostatic self-assembly of a polyoxometalate H_3 PW_(12)O_(4 O)(PW) and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone).PW can effectively regulate the self-assembling order of polymer moieties to form a large-ra nge lamellar structure,meanwhile,introducing protons into the nanoscale lamellar domains to build proton transport channels.Moreover,the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites.The lamellar nanocomposite exhibits a conductivity of 4.3 × 10~(-4) S/cm and a storage modulus of 1.1 × 10~7 Pa at room temperature.This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials.     

A novel imaging tool for hepatic portal system using phase contrast technique with hydrogen peroxide‐generated O2 gas

The objective of this study was to investigate the potential of hydrogen peroxide‐generated oxygen gas‐based phase contrast imaging (PCI) for visualizing mouse hepatic portal veins. The O₂ gas was made from the reaction between H₂O₂ and catalase. The gas production was imaged by PCI in real time. The H₂O₂ was injected into the enteric cavity of the lower sigmoid colon to produce O₂ in the submucosal venous plexus. The generated O₂ gas could be finally drained into hepatic portal veins. Absorption contrast imaging (ACI) and PCI of O₂‐filled portal veins were performed and compared. PCI offers high resolution and real‐time visualization of the O₂ gas production. Compared with O₂‐based ACI, O₂‐based PCI significantly enhanced the revealing of the portal vein in vivo. It is concluded that O₂‐based PCI is a novel and promising imaging modality for future studies of portal venous disorders in mice models.     

基于阿秒抖动光纤锁模激光器的时钟同步

光纤锁模激光器结构简单, 运转稳定, 且输出的超短脉冲序列具有极高的时钟稳定性, 在抽运探测、脉冲相干合成等要求高精度时钟同步的前沿领域有着广阔的应用前景. 本文通过激光器腔内的电光调制器进行反馈控制, 实现了两台光纤锁模激光器之间的紧密时钟信号同步; 并且通过平衡光学互相关方法, 对残余的时钟误差信号进行了测量, 分辨率达到了13 as. 通过优化激光器的腔内动力学过程及反馈环路的参数, 在[1 Hz, 10 MHz]的积分区间内得到了109 as的残余时钟误差, 对应单台激光器的平均时间抖动为77 as.     

Synthesis and Characterizations of Strongly Phosphorescent Copper(I) Halide Complexes with Bridged Bis[2-(diphenylphosphino)phenyl]ether Ligand

A series of strongly phosphorescent copper(I) halide complexes, namely [Cu(μ-X)POP]₂ (X = Cl (1), Br (2), I (3), Br_0.5Cl_0.5 (4), POP = bis[2-(diphenylphosphino)phenyl]ether), have been synthesized by reacting CuX with the diphosphine ligand in 1:1 molar ratio. All complexes were characterized by spectroscopic analysis (IR, UV–Vis), elemental analysis, and photoluminescence study. Single-crystal X-ray diffraction revealed that complex 2 is a dinuclear structure which is constructed by two μ-X bridges and two POP ligands as μ₂ bridges. Other complexes were determined as isologues of complex 2 by powder X-ray diffraction and elemental analysis. All complexes exhibit intense blue-green phosphorescence with a lifetime of ~1 μs in the solid state. The halogen-mixed complex presents a lightly change in the luminescence comparing to that of parent complexes. The excited states of all complexes have been assigned as halide-to-ligand charge transfer state mixed metal-to-ligand charge transfer character based on the time-dependent density functional theory calculations. All complexes are thermally stable according to thermogravimetric analysis so that they are suitable for applying in luminescent devices.     

Screening and analysis of metabolites in rat urine after oral administration of Apocynum venetum L. extracts using HPLC–TOF‐MS

HPLC with diode array detection and ESI‐TOF‐MS was used for the study of the constituents in Apocynum venetum L. extracts and the metabolites in rat urine after oral administration of A. venetum L. extracts. A formula database of the known constituents in A. venetum L. was established, and 21 constituents were rapidly identified by accurately matching their molecular masses with the formulae of the compounds in the database. Furthermore, 34 metabolites were detected and elucidated in the rat urine. The scientific and plausible biotransformation pathways of the flavonoid components in A. venetum L. were also proposed together with the presentation of clues for potential mechanisms of bioactivity. This specific and sensitive HPLC–ESI‐TOF‐MS method can be used to identify the chemical components in the extracts of A. venetum L. and their metabolites in rat urine. This method can also be used to reveal the possible metabolic mechanisms of action of the extract components in vivo.     

Synthesis and acaricidal activity of strobilurin-pyrimidine derivatives简

Pyriminostrobin, a new acaricide, was discovered in our previous studies. Because introducing fluorine into organic compounds can increase bioactivity, pyriminostrobin was modified as a series of strobilurin-pyrimidine derivatives for biological screening. The compounds were characterized by 1H NMR, MS and elemental analysis. Preliminary bioassays demonstrated that compounds 7e and 7i exhibited significant control against Tetranychus cinnabarinus （Boisd.） at 0.625 mg L^-1, and their acaricidal potencies were higher than pyriminostrobin in a greenhouse. The relationship between structure and acaricidal activity was also studied.