Ab initio Studies on the Reaction of M~ CH_4→M~ CH_2 H_2(M＝Sc,Y,La)

ＡｂｉｎｉｔｉｏＳｔｕｄｉｅｓｏｎｔｈｅＲｅａｃｔｉｏｎｏｆＭ~＋＋ＣＨ_４→Ｍ~＋ＣＨ_２＋Ｈ_２（Ｍ＝Ｓｃ，Ｙ，Ｌａ）ＺＨＵＲｏｎｇ－ｓｈｕｎ；ＤＡＩＳｈｕｓｈａｎ；ＨＵＡＮＧＪｉａｎ－ｈｕａａｎｄＹＥＳｏｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔ?..     

利用质谱－质谱法进行稠环芳烃化合物的结构解析

应用（ＥＩ）ＭＳ／Ｍｓ法研究了吡啶并苯并蒽酮以及苯并苯并蒽酮类异构体的裂解方式及其与结构之间的相关性，探讨了不同异构体中由Ｍ￣（ｉ＋）产生的［Ｍ－Ｈ］＋、［Ｍ－ＨＣＮ］＋、［Ｍ－ＣＯＨ］＋、［Ｍ－ＣＯ］（ｉ＋）、［Ｍ－（ＣＯ＋２Ｈ）］（ｉ＋）以及［Ｍ－（ＣＯ＋ＨＣＮ）］（ｉ＋）（ｉ＝１，２）等１价及２价离子在ＭＳ／ＭＳ－ＣＩＤ谱上的强度差异和裂解方式，发现是否含有氮原子以及氮原子和苯环位置的差异，是支配这类化合物在ＣＩＤ谱中裂解行为的主要因素。研究结果表明，２价离子的ＣＩＤ谱能更有效地反映这类杂环芳烃异构体之间的结构差异和裂解特性。     

Crystal Structure and Molecular Absolute Configuration of （＋）－Isocedranol （C_（15）H_（26）O）

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅａｎｄＭｏｌｅｃｕｌａｒＡｂｓｏｌｕｔｅＣｏｎｆｉｇｕｒａｔｉｏｎｏｆ（＋）－Ｉｓｏｃｅｄｒａｎｏｌ（Ｃ_（１５）Ｈ_（２６）Ｏ）￥ＬｉｕＪｉｅ；ＣｈｅｎＭｉｎ－Ｑｉｎ（ＣｅｎｔｅｒｏｆＡｎａｌｙｓｉｓ＆Ｍｅａｓｕｒｅｍ...     

A SIMPLE SYNTHESIS OF (+)-ACETYLGONIOTRIOL

ＡＳＩＭＰＬＥＳＹＮＴＨＥＳＩＳＯＦ（＋）－ＡＣＥＴＹＬＧＯＮＩＯＴＲＩＯＬ￥ＺｈｉＣａｉＹＡＮＧａｎｄＷｅｉＳｈａｇＺＨＯＵ￣＊（ＳｈａｎｇｈａｉＩｎｓｔｉｔｕｔｅｏｆＯｒｇａｎｉｃＣｈｅｍｉｓｔｒｙ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅ...     

The Crystal Structure of Hexamolybdenum Halide NaMo_6X_9C_（l4）（X＝Cl_n＋I_（1－n）） by Solid State Reaction

ＴｈｅＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＨｅｘａｍｏｌｙｂｄｅｎｕｍＨａｌｉｄｅＮａＭｏ_６Ｘ_９Ｃ_（ｌ４）（Ｘ＝Ｃｌ_ｎ＋Ｉ_（１－ｎ））ｂｙＳｏｌｉｄＳｔａｔｅＲｅａｃｔｉｏｎ￥ＧｕｏＧｕｏ－Ｃｏｎｇ；ＺｈｕａｎｇＨｏｎｇ－Ｈｕｉ；ＷａｎｇＭａｎ?..     

利用质谱—质谱法进行稠环芳烃化合物的结构解析

应用（ＥＩ）ＭＳ／ＭＳ法研究了吡啶并苯并蒽酮以及苯并苯并蒽酮类异构体的裂解方式及其与结构之间的相关性，探讨了不同异构体中由Ｍ＾ｉ＋产生的［Ｍ－Ｈ］＾＋、［Ｍ－ＨＣＮ］＾＋、［Ｍ－ＣＯＨ］＾＋、［Ｍ－ＣＯ］＾ｉ＋、［Ｍ－（ＣＯ＋２Ｈ）］＾ｉ＋以及［Ｍ－（ＣＯ＋ＨＣＮ）］＾ｉ＋（ｉ＝１，２）等１价及２价离子在ＭＳ／ＭＳ－ＣＩＤ谱上的强度差异和裂解方式，发现是否含有氮原子以及氮原子和苯环位置的差异，是支     

几个分子和负离子的QCI势能曲线

用ＱＣＩＳＤ（Ｔ）／６３１１＋Ｇ（３ｄｆ，２ｐ）（简称ＱＣＩ）计算了ＢＨ－（２Π），ＢＦ－（２Π），ＢＨ（１∑），ＢｅＨ－（１∑），ＢｅＦ－（１∑）和ＢＦ（１∑）的较完整的势能曲线，探讨了这些体系的稳定性和解离过程．同时用Ｍｏｒｓｅ函数和ＥＲ函数拟合得到势能曲线，用拟合结果计算谐性频率和非谐性频率，并与已有的实验数据（ＢＨ和ＢＦ分子）进行比较，由此考察了ＱＣＩ理论方法在远离平衡构型时的可靠性．对于因单参考态近似导致的反常势能曲线进行了ＣＡＳＳＣＦ计算．还比较了ＱＣＩ和Ｇ２理论中标准的ＭＰ２（ｆｕｌ）／６３１平衡几何构型及其对ＱＣＩ总能量的影响．     

STUDIES ON MACROCYCLIC DITERPENOIDS（XI）──A Convergent and Stereoselective Synthesis of Cembrenene Precursor－4，10－Dimethyl－7－Isopropenyl－14－Oxo－3Z，5E，10E－Pentadecatrienal

ＳＴＵＤＩＥＳ　ＯＮ　ＭＡＣＲＯＣＹＣＬＩＣ　ＤＩＴＥＲＰＥＮＯＩＤＳ（ＸＩ）──Ａ　Ｃｏｎｖｅｒｇｅｎｔ　ａｎｄ　Ｓｔｅｒｅｏｓｅｌｅｃｔｉｖｅ　Ｓｙｎｔｈｅｓｉｓ　ｏｆ　Ｃｅｍｂｒｅｎｅｎｅ　Ｐｒｅｃｕｒｓｏｒ－４，１０－Ｄｉｍｅｔｈｙｌ－７－Ｉ...     

离子浮选石墨炉原子吸收光谱法测定水中痕量Cr（Ⅵ）／Cr（Ⅲ）

本文以二苯卡巴肼（ＤＰＣＩ）和十二烷基硫酸钠（ＳＬＳ）为浮选剂研究了分离浓缩（Ｃｒ（Ⅵ）的最佳条件，建立了水中痕量络的形态分析方法。该方法简单、快速、检测限０．０３μｇＬ＾－１，变异系九小于４％，２００ｍＬ水样中含ＮＯ３５０，Ｎａ＾＋，Ｍｇ＾２＋４０，Ｃｌ２８，Ｄ，Ｃａ＾２＋，ＳＯ４１０，ＣＯ３９，Ａｌ＾２＋，Ｃｏ＾２＋，Ｎｉ６２＋５，Ｍｎ＾２，Ｐｂ＾２＋２．５，Ｆｅ＾３＋０．２ｍｇ不影响测定。方     

Synthesis and Magnetism of 2-Hydroxy-1,3-propylene-bis(oxamato)-bridged Co~ⅡCu~ⅡCo~Ⅱ Complexes

ＳｙｎｔｈｅｓｉｓａｎｄＭａｇｎｅｔｉｓｍｏｆ２┐Ｈｙｄｒｏｘｙ┐１，３┐ｐｒｏｐｙｌｅｎｅ┐ｂｉｓ（ｏｘａｍａｔｏ）┐ｂｒｉｄｇｅｄＣｏⅡＣｕⅡＣｏⅡＣｏｍｐｌｅｘｅｓＭＩＡＯＭｉｎｇ－ｍｉｎｇ，ＣＨＥＮＧＰｅｎｇ，ＬＩＡＯＤａｉ－ｚｈｅｎｇＪＩＡ...     

SIMS investigation of CrN sputtercoatings

Chromium nitride layers produced by reactive sputtering with different process parameters were characterized with EPMA, SIMS depth profiling, and three-dimensional SIMS imaging. EPMA results are used to quantify the major components of the films while SIMS is used to gather information about the distribution of the elements chromium, silicon, nitrogen, and oxygen. For all measurements a Cs+ primary ion beam was applied to sputter the sample. Positive MCs+ (M represents the element to be analyzed) secondary ions were detected. SIMS depth profiling shows an even distribution of all major elements except oxygen, which shows significant differences in concentration and distribution depending on the process parameters. CrN layers produced at low sputter power have much higher concentration of oxygen than layers produced with high sputter power. Heating the silicon substrate during the process results in an enrichment of oxygen at the interface.     

Ga‐focused ion beam time‐of‐flight secondary ion mass spectrometer analysis of the grain boundary segregation/precipitation of boron in steel

Ga‐focused ion beam time‐of‐flight secondary ion mass spectrometry (FIB‐TOF‐SIMS) analysis was performed to investigate the grain boundary segregation/precipitation of boron in steel. To overcome the low secondary ion yield from the primary Ga⁺ source and the sensitivity using a high‐resolution Ga‐FIB source, a low energy oxygen ion beam was used prior to the Ga‐FIB‐TOF‐SIMS analysis. As a result, it was found that Ga‐FIB‐TOF‐SIMS is a very powerful tool for mapping boron segregation and/or precipitation in steel with a spatial resolution of ~200 nm. In addition, the results were strongly dependent on the surface composition. Copyright © 2014 John Wiley & Sons, Ltd.     

Fission track–secondary ion mass spectrometry as a tool for detecting the isotopic signature of individual uranium containing particles

A fission track technique was used as a sample preparation method for subsequent isotope abundance ratio analysis of individual uranium containing particles with secondary ion mass spectrometry (SIMS) to measure the particles with higher enriched uranium efficiently. A polycarbonate film containing particles was irradiated with thermal neutrons and etched with 6 M NaOH solution. Each uranium containing particle was then identified by observing fission tracks created and a portion of the film having a uranium containing particle was cut out and put onto a glassy carbon planchet. The polycarbonate film, which gave the increases of background signals on the uranium mass region in SIMS analysis, was removed by plasma ashing with 200 W for 20 min. In the analysis of swipe samples having particles containing natural (NBL CRM 950a) or low enriched uranium (NBL CRM U100) with the fission track–SIMS method, uranium isotope abundance ratios were successfully determined. This method was then applied to the analysis of a real inspection swipe sample taken at a nuclear facility. As a consequence, the range of ²³⁵U/²³⁸U isotope abundance ratio between 0.0276 and 0.0438 was obtained, which was higher than that measured by SIMS without using a fission track technique (0.0225 and 0.0341). This indicates that the fission track–SIMS method is a powerful tool to identify the particle with higher enriched uranium in environmental samples efficiently.     

Thermal desorption characteristics of ammonium nitrate and potassium perchlorate inorganic salts using particle mapping time‐of‐flight secondary ion mass spectrometry

To help optimize ion mobility spectrometry (IMS) for the detection of inorganic explosives, time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was used to study the thermal desorption behavior of ammonium nitrate (NH₄NO₃) and potassium perchlorate (KClO₄) particles on surface. This was carried out by ToF‐SIMS chemical imaging analysis to identify the change in the number of particles and their size before and after exposure to desorption temperatures of 150, 200, 250, 300, 350 and 400 °C for durations of 3, 6, 9 and 12 s. It was found that particles less than 7.2 µm in diameter contributed to more than 50% of both the number and mass of the particles desorbed from the surface. Combining ToF‐SIMS particle mapping with the vapor collection experiment revealed that the technique could be used also to determine the optimum desorption temperatures of explosive particles; this was found to be approximately 200 and 300 °C for NH₄NO₃ and KClO₄ particles, respectively. Although work remains to validate this number for KClO₄, experiments using variable desorption temperature IMS suggest the optimum temperature of NH₄NO₃ desorption to be approximately 200 °C. Published 2016. This article is a U.S. Government work and is in the public domain in the USA     

Precise and fast secondary ion mass spectrometry depth profiling of polymer materials with large Ar cluster ion beams

We demonstrate depth profiling of polymer materials by using large argon (Ar) cluster ion beams. In general, depth profiling with secondary ion mass spectrometry (SIMS) presents serious problems in organic materials, because the primary keV atomic ion beams often damage them and the molecular ion yields decrease with increasing incident ion fluence. Recently, we have found reduced damage of organic materials during sputtering with large gas cluster ions, and reported on the unique secondary ion emission of organic materials. Secondary ions from the polymer films were measured with a linear type time‐of‐flight (TOF) technique; the films were also etched with large Ar cluster ion beams. The mean cluster size of the primary ion beams was Ar₇₀₀ and incident energy was 5.5 keV. Although the primary ion fluence exceeded the static SIMS limit, the molecular ion intensities from the polymer films remained constant, indicating that irradiation with large Ar cluster ion beams rarely leads to damage accumulation on the surface of the films, and this characteristic is excellently suitable for SIMS depth profiling of organic materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Reduction of matrix effects in TOF‐SIMS analysis by metal‐assisted SIMS (MetA‐SIMS)

We investigated reduction of the matrix effect in time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) analysis by the deposition of a small amount of metal on the sample surfaces (metal‐assisted SIMS or MetA‐SIMS). The metal used was silver, and the substrates used were silicon wafers as electroconductive substrates and polypropylene (PP) plates as nonelectroconductive substrates. Irganox 1010 and silicone oil on these substrates were analyzed by TOF‐SIMS before and after silver deposition. Before silver deposition, the secondary ion yields from the substances on the silicon wafer and PP plate were quite different due to the matrix effect from each substrate. After silver deposition, however, both ion yields were enhanced, particularly the sample on the PP plate, and little difference was seen between the two substrates. It was therefore found that the deposition of a small amount of metal on the sample surface is useful for reduction of the matrix effect. By reducing the matrix effect using this technique, it is possible to evaluate from the ion intensities the order of magnitude of the quantities of organic materials on different substrates. In addition, this reduction technique has clear utility for the imaging of organic materials on nonuniform substrates such as metals and polymers. MetA‐SIMS is thus a useful analysis tool for solving problems with real‐world samples. Copyright © 2005 John Wiley & Sons, Ltd.     

SIMS: from research to production control

In 1958, when I joined the Philips Research Laboratories, there were a number of technological problems related to the analysis of solids within Philips that needed analytical support. Because the available (bulk) techniques did not give sufficient results, a new technique, later called secondary ion mass spectrometry (SIMS), was launched that involved the bombardment of a solid target with (primary) energetic ions, followed by mass analysis and ion detection of the sputtered (secondary) target ions. The restrictions of the available infrastructure for such an analytical technique were many: there was no PC for data handling, no internet or database for literature search, the photocopying machine was not yet invented, communication with other scientists had to be done by mail (there was no fax, no E‐mail, no mobile phones) and, what was worse, SIMS was not considered to be a useful analytical technique compared with established techniques! In the years that followed there were many advances:

• (1) The SIMS instrumentation was improved by better ion optics, advanced electronic equipment and was extended from sector type to quadrupole and finally to time‐of‐flight (TOF) mass spectrometers.
• (2) The methodology of SIMS was developed step by step (parameters such as lateral and depth resolution, detection limit and quantitative analysis were all optimized in turn).
• (3) The SIMS technique then made its entrance to solve problems in technology development.

In the last two decades SIMS has become an indispensable, reliable, quantitative analytical technique for production control in integrated circuit technology and the after‐sales care of integrated circuits. The philosophy of the provision of an analytical service at the Philips Research Laboratory (hereinafter referred to as ‘our laboratory’) is discussed. After the initial period, where every method (SIMS, AES, ESCA, RBS, etc.) was claimed to be ‘the only one’ (the panacea), we learned how to organize analytical service cost efficiently and for the optimum benefit of the ‘customer’. The core analytical techniques were concentrated in one department and the customer would profit from synergy by using several appropriate analytical techniques for the same problem. Today, the latest developments in SIMS instrumentation keep pace with the latest challenges of the ultra‐large‐scale integration (ULSI) roadmap for integrated circuits, which indicates the dimensions of the circuits that are predicted for the years to come. Copyright © 2003 John Wiley & Sons, Ltd.     

Molecular ME‐ToF‐SIMS yield as a function of DHB matrix layer thicknesses obtained from brain sections coated by sublimation/deposition techniques

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) can be used to image biological samples with nanometer‐scale resolution, albeit with the drawback that it often cannot detect large molecular signals. One way to increase secondary ion molecular yield is to chemically modify the surface in the so‐called matrix‐enhanced SIMS (ME‐SIMS) approach, which is based on embedding analyte molecules in low‐weight organic matrices. In this study, a solvent‐free sample preparation technique was employed using sublimation/deposition for coating a mouse brain section with a thin layer of a 2,5‐dihydroxybenzoic acid (DHB) matrix. Using this preparation technique, signal enhancements of up to a factor of 18 could be detected. It was found that the matrix layer thickness plays an important role in the efficiency of yield enhancement. Also, a complex influence of the matrix layer on various signals was observed. Copyright © 2015 John Wiley & Sons, Ltd.     

Direct analysis of lipids in mouse brain using electrospray droplet impact/SIMS

Electrospray droplet impact (EDI)/secondary ion mass spectrometry (SIMS) is a new desorption/ionization technique for mass spectrometry in which highly charged water clusters produced from the atmospheric‐pressure electrospray are accelerated in vacuum by 10 kV and impact the sample deposited on the metal substrate. EDI/SIMS was shown to enhance intact molecular ion formation dramatically compared to conventional SIMS. EDI/SIMS has been successfully applied to the analysis of mouse brain without any sample preparation. Five types of lipids, i.e. phosphatidylcholine (PC), phosphatidylserine, phosphatidylinositol (PI), galactocerebroside (GC) and sulfatide (ST), were readily detected from mouse brain section. In addition, by EDI/SIMS, six different regions of the mouse brain (cerebral cortex, corpus callosum, striatum, medulla oblongata, cerebellar cortex and cerebellar medulla) were examined. While GCs and STs were found to be rich in white matter, PIs were rich in gray matter. Copyright © 2010 John Wiley & Sons, Ltd.     

Direct profiling of saccharides,organic acids and anthocyanins in fruits using electrospray droplet impact/secondary ion mass spectrometry

Electrospray droplet impact (EDI)/secondary ion mass spectrometry (SIMS) is a new desorption/ionization technique for mass spectrometry in which highly charged water clusters produced from atmospheric‐pressure electrospray are accelerated in vacuum by several kV and impact on the sample deposited on the metal substrate. In this study, we applied EDI/SIMS directly to fruits, such as bananas, strawberries, grapes and apples. The major components in the fruits – fructose, glucose, sucrose and organic acids – could be observed with strong signal intensities. EDI/SIMS was also applied to the analysis of different regions of strawberries and apples. Compared with matrix‐assisted laser desorption/ionization (MALDI), ion signals with lower background signals could be obtained, particularly for the low molecular weight analytes. Copyright © 2010 John Wiley & Sons, Ltd.