离子—分子反应及其在质谱分析中的应用

利用离子—分子反应 ,不仅可以提供分子离子峰 ,而且可以提高检测的灵敏度 ,了解分子的结构特征。本文根据离子—分子反应的机理 ,介绍了金属离子的亲和力的测定方法和金属离子在化合物上的加合位点 ,并阐述了离子—分子反应在化学电离质谱 ( CI-MS)、碱金属离子化学电离质谱 ( ACI-MS)、电喷雾电离质谱 ( ESI-MS)、快原子轰击质谱 ( FAB-MS)、以及基质辅助激光解吸电离质谱 ( MALDI-MS)

Separation of Ions from Volatile Organic Compounds Using High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometer

A combination of high-field asymmetric waveform ion mobility spectrometry （FAIMS） with mass spectrometer （MS） was analyzed. FAIMS separates ions from the volatile organic compounds in the gas-phase as an ion-filter for MS. The sample ions were created at ambient pressure by ion source, which was equipped with a 10.6 eV UV discharge lamp （A=116.5 nm）. The drift tube of FAIMS is composed of two parallel planar electrodes and the dimension is 10 mm×8 mm×0.5 mm. FAIMS was investigated when driven by the high-filed rectangular asymmetric waveform with the peak-to-peak voltage of 1.36 kV at the frequency of 1 MHz and the duty cycle of 30%. The acetone, the butanone, and their mixture were adopted to characterize the FAIMS-MS. The mass spectra obtained from MS illustrate that there are ion-molecular reactions between the ions and the sample neutral molecular. And the proton transfer behavior in the mixture of the acetone and the butanone is also observed. With the compensation voltage tuned from -30 V to 10 V with a step size of 0.1 V, the ion pre-separation before MS is realized.

Electron Attachment Studies for CHCl3 Using Ion Mobility Spectrometry

The dissociative electron attachment process for CHCl3 at different electric field have been studied with nitrogen as drift and carrier gas using corona discharge ionization source ion mobility spectrometry （CD-IMS）. The corresponding electron attachment rate constants varied from 1.26×10-8 cm3/（molecules s） to 8.24×10-9 cm3/（molecules s） as the electric field changed from 200 V/cm to 500 V/cm. At a fixed electric field in the drift region, the attachment rate constants are also detected at different sample concentration. The ionmolecule reaction rate constants for the further reaction between Cl^- and CHCl3 are also detected, which indicates that the technique maybe becomes a new method to research the rate constants between ions and neural molecules. And the reaction rate constants between Cl- and CHCl3 are the first time detected using CD-IMS.

Quasi-classical Trajectory Study on the H^＋＋H2 Reaction

Quasi-classical trajectory （QCT） calculations on the H^＋＋H2 reaction system were carried out on a new potential energy surface （PES）. Theoretical calculations show that the angular distribution of the forward and backward products is roughly symmetric for the title reaction. The product rotational state distribution was also determined at a few collision energies. In t, he collision energy range from 0.124 eV to 1.424 eV, the integral cross section for this system monotonically decreases with the collision energy. A comparison with the experimental result of the ion-molecule reaction was also made, the agreement is generally good.

Oxidation of p/o-Cresols to p/o-Hydroxybenzaldehydes Catalyzed by Metalloporphyrins with Molecular Oxygen

The two novel green oxidation processes of p/o-cresols to p/o-hydroxybenzaldehydes catalyzed by metalloporphyrins in the presence of molecular oxygen were developed in this work.Among the metalloporphyrins with different central ions and substituents studied,T(p-NO 2)PPCoCl and T(p-OCH 3)PPFeCl presented the highest activities for p-cresol and o-cresol oxidation reactions respectively.The molar ratio of sodium hydroxide to cresols and different reaction parameters including reaction temperature,reaction time and reaction pressure have been investigated,and 69.8%/50.4% conversions of p/o-cresol and 86.6%/26.6% selectivities for p/o-hydroxybenzaldehydes were reached under optimized conditions.

Ar/N2/CH4 Glow Discharge at Low Pressures

Ar/N2/CH4 glow discharge at low-pressure are studied in a closed system. The plasma was produced in 79.6% N2-15.4% Ar- 5.0% CH4 ternary mixture at pressures between 0.5 and 10.0 Torr. The diagnostic has been made by optical emission spectroscopy （OES）. The principal species observed were： N2, N2＋, CH＋, CN, C2, C3, HI3, Ha, C＋ and At. It presents the behaviour of the bands and lines intensities as a function of the pressure. Also, it displays the ratios of intensities of N＋2 （391.44 nm）, CN （392.08 nm）, and H （486.13 nm） to that of the N2 （337.13 rim） as function of pressure. The ratios show a slow decreasing behavior as a function of the pressure. Being the CH/N2 ratio more highest and H/N2 ratio the lowest one. The variations of excited species at different pressures may change the subsequent chemical reactions in the gas phase significantly. The present results suggest that the ion-molecule and molecule-molecule reactions in the gas phase are likely to play a dominant role in the present pressures.

New tetraphenylpyridinium-based luminogens with aggregation-induced emission characteristics

The research on aggregation-induced emission (AIE) has drawn increasing interests in the past decade. With the efforts scientists paid, a variety of AIE systems have been developed, among which the tetraphenylethelene and silole derivatives are the most studied. Development of new AIE systems could further enrich the AIE molecules and promote the development of AIE area. In this communication, we prepared a new AIE system based on 1,2,4,6-tetraphenylpyridinium ions according to the restriction of intramolecular rotation mechanism. These molecules could be facilely synthesized via one-step and one-pot reaction. The ionic AIE-active molecules could find wide application in sensing and optoelectronic areas.

Cu2O-Au Nanocomposites with Novel Structures and Remarkable Chemisorption Capacity and Photocatalytic Activity

The decomposition of Cull nanoparticles in aqueous solution has been successfully developed as a novel method for the preparation of Cu2O nanoparticles. In particular, we found that the decomposition of Cull nanoparticles in aqueous solution could be catalyzed by Au colloids, forming CU2O-Au nanocomposites. The composition and structure of the resulting Cu2O-Au nanocomposites have been characterized in detail by inductively coupled plasma atomic emission spectroscopy, powder X-ray diffraction, N2 adsorption-desorption isotherms, infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. Their visible-light-driven photocatalytic activity toward various dye molecules has also been investigated. Depending on the Au：Cu ratio, Cu20-Au nanocomposites exhibit different novel nanostructures including a beautiful flower-like nanostructure that consists of polycrystalline Cu2O, amorphous Cu2O and Au colloids. We propose that the rapidly-generated bubbles of H2 during the course of the catalytic decomposition reaction drive the simultaneously-formed Cu2O to form amorphous curved thin foils and might also act as a template to assemble curved thin foils of amorphous Cu2O, polycrystalline Cu2O and Au colloids into uniform nanostructures. A Cu2O-Au nanocomposite with a Cu：Au ratio of 40 exhibits remarkable chemisorption capacity and visible-light-driven photocatalytic activity towards methyl orange and acid orange 7 and is a promising chemisorption-photocatalysis integrated catalyst. The catalytic decomposition of the metal hydride might open up a new approach for the fabrication of other metal/metal oxide nanocomposites with novel nanostructures and properties.