聚芴类发光材料合成中间体的质谱分析

利用电喷雾电离（ESI）质谱－质谱（MS－MS）技术，分析了新化合物2，7－双（4，4，5，5－四甲基－1，3，2－二氧杂硼烷－2－基）－9，9－二辛基芴的EI和ESI的质谱，确认了该谱图中母离子和子离子的关系，讨论了其碎裂途径，为其结构鉴定提供了依据。     

N—环已基吡嗪酮类化合物的EI质谱及其解析

总结和归属了（2H）－2－环已基－3，4二氢吡咯并[1,2-α]吡嗪－1－酮及其7个苯甲酰基衍生物和3个苯乙酰基衍生物在电子轰击电离质谱（EI－MS）中的主要裂解方式和特征，指明了主要碎片离子的来源和结构，这10个芳酰基衍生物质谱图中的主要碎片峰均来自麦氏重排和异构化后的α－裂解，由其裂解产生的m/z120和m/z163离子是该类化合物共同的特征离子；吡嗪酮苯甲酰基衍生物基峰为M－82，苯乙酰基类衍生物基峰为m/z245。     

丙硫咪唑的离子／中性碎片复合物中间体质谱破裂

报道了丙硫咪唑（５－丙硫基－苯并咪唑－２氨基甲酸酯）的电子轰击质谱。利用串联质谱的低能碰撞诱导解离（ＣＩＤ）技术研究了此化合物的单分子解离，并提出了可能的离子／中性碎片复合筘间体碎裂机理，用来解释在质谱碎裂过程中出现的氢迁移（尤其是远距离的氢迁移）现象。     

脂肪族双酰基二酰二肼类化合物的EI质谱特征

总结和归属了N，N′－二乙酰基丁二酰二肼，N，N′－二乙酰基癸二酰 二肼以及4种N，N′－二酰基戊二酰二肼和4种N，N′－二酰基己二酰二肼共10个化合物在电子轰击电离质谱（EIMS）中的主要裂解方式和特征，指明了主要碎片离子的来源和结构；这10种化合物质谱图中的主要碎片峰均来自于羧基的α－裂解和重排α－裂解，由其裂解产生的基峰离子H2NNHCO（CH2）nC≡0^ 以及RCONHNHCO（CH）nC≡0,RCONHN^ H3等离子是该类化合物共同的特征离子。     

GC-Q/TOF MS技术快速鉴定防风挥发油中的成分

采用气相色谱－四极杆飞行时间串联质谱（GC－Q/TOF MS）技术对中药防风挥发油中的化学成分进行鉴定。首先在标准EI电离源模式下采集样品,通过定性软件对数据进行解卷积和NIST库比对,鉴定出库内化合物82种,包括烃类、醛酮类、醇类、酸类和酯类。此外,采用GC－Q/TOF MS的低能量电离源（Lower energy）模式,确定未知化合物的分子离子峰;采集二级质谱,获得碎片离子信息,推断分子式,并结合Chemspider数据库,鉴定了未知物结构。运用该方法鉴定出NIST库外化合物2种,分别为（5E,7E,11S）-5,11-二甲基-5,7-十四碳二烯-1-炔-4-醇和（6S,7E,9E）-7,9-十七碳二烯-11,13-炔-6-醇。同时鉴定了库内化合物3种,为2,4-癸二烯醛、肉豆蔻酸和棕榈酸甲酯,与自动匹配结果相一致,验证了该方法的可行性。综上,从防风挥发油中共鉴定出84种化学成分。该研究丰富了GC－Q/TOF MS在中药防风挥发油中的运用,也为其他物质的快速全面鉴定提供了新思路,尤其是GC－Q/TOF MS的Lower energy 和MS/MS联用模式适用于NIST库中未收录化合物的准确快速鉴定。     

稀土二茂铁甲酸配合物的研究

合成了１５种稀土元素的二茂铁甲酸配合物，对其进行了元素分析、质谱、溶液电导、Ｘ－射线粉末衍射、付立叶红外光谱的研究。结果表明配合物的组成为：（η￣５Ｃ＿５Ｈ＿５Ｆｅη￣５Ｃ＿５Ｈ＿４ＣＯＯ￣－）＿３·Ｌｎ·Ｈ＿２Ｏ，（Ｌｎ＝Ｌａ～Ｌｕ及Ｙ，ｐｍ除外），且均为类质同晶化合物，ＣＯＯ￣－都以螯合方式与Ｌｎ￣（３＋）配位，在红外光谱中观察到明显的“Ｌｎ系效应”。     

N,N-二取代甘氨酸酯的ESI-MS/MS研究

应用多级质谱（＋）ESI—MS／MS考察了八种N,N-二取代甘氨酸酯化合物的质谱行为,并对其质谱裂解途径进行解析,为表征该类化合物提供了依据。     

聚甘油脂肪酸酯的结构鉴定

该文采用傅里叶变换离子回旋共振质谱（FT－ICR－MS）、核磁共振氢谱（1H NMR）以及气相色谱－质谱（GC－MS）技术,对聚甘油脂肪酸酯的结构进行鉴定。样品溶解后进行FT－ICR－MS测定,根据精确分子离子数据,推测出聚甘油脂肪酸酯的基本结构以及甘油的聚合度,并采用1H NMR进行了验证。将聚甘油脂肪酸酯水解后,对脂肪酸部分进行甲酯化,经正庚烷萃取,由GC－MS测定,分析脂肪酸的组成。综合以上结果最终确定了聚甘油脂肪酸酯的结构。该研究为聚合物的结构鉴定提供了一种新的思路和方法。     

芳氨基硫脲类化合物的质谱研究（Ⅱ）

本文报道了五种新的芳氨基硫脲类化合物，即１－（４－溴－２－羧基苯基）－４－烷基氨基硫脲的电子轰击质谱（ＥＩＭＳ）。结果表明，该类化合物的分子离子峰（Ｍ＋）很弱，但却具有效强的［Ｍ－Ｈ］＋峰。分子离子的断裂以Ｎ－Ｎ键和Ｃ－Ｎ键的断裂为主，并伴随着六员环或四员环过渡态氢重排，生成相应的芳氨基正离子和芳肼基正离子，这两种离子继续失水或失其它小分子，从而形成一系列特征离子，包括骨架重排离子。     

芳香硝基化合物的能量分辨质谱

本文报道用ＭＳ／ＭＳ技术的一种重要实验方法——能量分辨质谱（ＥＲＭＳ）来鉴别质谱分析中的同分异构体化合物。系统探讨了同分异构的硝基芳香化合物２，３－ＤＮＴ和３，５－ＤＮＴ（相对分子质量为１８２）在电子轰击（ＥＩ）方式下，裂分途径与其分子内能的相互关系以及离子的结构和裂分途径相对于碰撞能量（ＣＥ）的依赖关系（裂分曲线）。结果表明，利用同分异构化合物在能量分辨中的显著差异可以辨别它们的结构     

Indacyclopentadienes and Aromatic Indacyclopentadienyl Dianions: Synthesis and Characterization

A series of unprecedented metallacycles of indium, including indacyclopentadienes ( 2 ), spiro indacyclopentadienes ( 3 ), aromatic indacyclopentadienyl dianions with an In−Li bond ( 4 ), and aromatic indacyclopentadienyl dianions with an In−In bond ( 5 ), were synthesized and structurally characterized by single-crystal X-ray structural analysis for the first time. Both indacyclopentadienes 2 and 3 were synthesized by reaction of 1,4-dilithio-1,3-butadienes with InCl₃. Structural transformations between 2 and 3 were observed. Reduction of indacyclopentadienes 2 with an excess amount of lithium afforded aromatic indacyclopentadienyl dianions 4 with an In−Li bond or 5 with an In−In bond, respectively, depending on the substituents on the ring. The aromatic character of 4 and 5 was confirmed by both experimental measurements and theoretical analysis.     

3种方法测定植物源性农产品中霉灵残留量

建立了测定大豆、糙米、黄瓜、甜菜等6种植物源性农产品中(噁)霉灵残留的气相色谱-火焰光度法(GC-FPD)、气相色谱-氮磷检测法(GC-NPD)和液相色谱-串联质谱法(LC-MS/MS).GC-FPD法采用丙酮-正己烷提取样品,O,O-二甲基硫代磷酰氯衍生,GC-FPD分析,外标法定量;GC-NPD法采用丙酮-正己烷提取样品,十八烷基键合硅胶(C18)净化,GC-NPD分析,外标法定量;LC-MS/MS法,样品采用乙腈提取,石墨化碳黑(GCB)净化,LC-MS/MS分析,基质匹配外标法定量.结果表明,(噁)霉灵的响应值与其浓度间呈良好的线性关系,3种方法的相关系数均大于0.998.在3个加标浓度下,GC-FPD法中(噁)霉灵的日间平均回收率为82%~96%,日间相对标准偏差(RSD)为3.4%~12.1%,方法的定量下限为0.25 mg/kg (甜菜为0.05 mg/kg);GC-NPD法的日间平均回收率为81%~103%,日间RSD为4.1%~14.3%,定量下限为0.25 mg/kg (甜菜为0.05 mg/kg);LC-MS/MS法的日间平均回收率为74%~110%,日间RSD为2.5%~10.7%,定量下限为0.05 mg/kg.3种方法均具有良好的准确性和稳定性,可满足(噁)霉灵残留分析的要求.     

In3+-doped TiO2 and TiO2/In2S3 nanocomposite for photocatalytic and stoichiometric degradations

A novel In(3+)-doped TiO(2) and TiO(2)/In(2)S(3) nanocomposites for photocatalytic degradation of environmental pollutants and stoichiometric degradation of warfare agents were prepared by a homogeneous hydrolysis with urea and thioacetamide, respectively. The prepared samples series TiInTAA were annealed at 600°C. The prepared samples were characterized by X-ray powder diffraction, IR spectroscopy, Raman spectroscopy, specific surface area (BET) and porosity determination. The method of UV-Vis diffuse reflectance spectroscopy was employed to estimate band-gap energies. The photocatalytic activity (PCA) was tested by degradation of Orange dye, whereas stoichiometric activity was studied by degradation of sulfur mustard. Incorporation of In(3+) into titania lattice increases PCA of TiO(2) in the visible light and increases stoichiometric decomposition of sulfur mustard against nondoped TiO(2) as well. PCA of TiO(2)/In(2)S(3) composite depends on the optimal ratio of TiO(2):In(2)S(3) in composite, while the activity for stoichiometric decomposition of sulfur mustards depends on the content of In(2)S(3) in nanocomposite.     

Density functional theory simulations of amorphous high-κ oxides on a compound semiconductor alloy: a-Al2O3/InGaAs(100)-(4×2), a-HfO2/InGaAs(100)-(4×2), and a-ZrO2/InGaAs(100)-(4×2)

The structural properties of a-Al(2)O(3)∕In(0.5)Ga(0.5)As, a-HfO(2)∕In(0.5)Ga(0.5)As, and a-ZrO(2)∕In(0.5)Ga(0.5)As interfaces were investigated by density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic amorphous a-Al(2)O(3), a-HfO(2), and a-ZrO(2) samples were generated using a hybrid classical-DFT MD "melt-and-quench" approach and tested against the experimental properties. For each stack type, two systems with different initial oxide cuts at the interfaces were investigated. All stacks were free of midgap states, but some had band-edge states which decreased the bandgaps by 0%-40%. The band-edge states were mainly produced by deformation, intermixing, and bond-breaking, thereby creating improperly bonded semiconductor atoms. The interfaces were dominated by metal-As and O-In∕Ga bonds which passivated the clean surface dangling bonds. The valence band-edge states were mainly localized at improperly bonded As atoms, while conduction band-edge states were mainly localized at improperly bonded In and Ga atoms. The DFT-MD simulations show that electronically passive interfaces can be formed between high-κ oxides dielectrics and InGaAs if the processing does not induce defects because on a short time scale the interface spontaneously forms electrically passive bonds as opposed to bonds with midgap states.     

Surface chemistry study of RuO2/IrO2/TiO2 mixed-oxide electrodes

DSA metal oxide electrodes such as the RuO(2)/IrO(2)/TiO(2) mixed system are widely studied for their excellent electrocatalytic activity. In order to understand their catalytic properties, the comprehension of the surface chemistry involved during electrochemical treatments is crucial. With this aim, RuO(2)/IrO(2)/TiO(2) mixed-oxide electrodes having various noble metal contents were studied by means of secondary ion mass spectrometry (SIMS). In particular, cathodic and anodic polarization and O(2) evolution reactions were carried out to test the electrode behaviour and SIMS analyses were performed after all these treatments. In this way, surface changes induced by electrochemical treatments and depending on electrode composition were widely investigated by SIMS, revealing, for example, the presence of hydration or preferential dissolution phenomena induced by electrochemical processing.     

Urea-based hydrothermal growth, optical and photocatalytic properties of single-crystalline In(OH)3 nanocubes

Nearly monodisperse single-crystalline In(OH)(3) nanocubes were successfully synthesized using In(NO(3))(3) x 4.5 H(2)O as indium source in the presence of urea and cetyltrimethyl ammonium bromide (CTAB) by a two-step hydrothermal process: the stock solution was heated at 70 degrees C for 24 h and then at 120 degrees C for 12 h. The structure and morphology of the resultant In(OH)(3) samples were determined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results revealed that most of as-synthesized In(OH)(3) nanocubes were uniform in size, with the average edge length of approximately 700 nm. The influences of the reaction temperature, the reaction time, the mineralizer, and the surfactant on the morphology of the obtained products were discussed in detail. Room-temperature photoluminescence (PL) spectrum of the In(OH)(3) nanocubes showed a peculiar strong emission peak centered at 480 nm. Furthermore, the photocatalytic properties of the In(OH)(3) nanocubes were tested. It was found that In(OH)(3) exhibited not only higher activity for benzene removal, but also better H(2) evolution from water than the commercial Degussa P25 TiO(2).     

p-CuO/n-In_2O_3异质结纳米纤维的制备及气敏特性

以电纺In_2O_3纳米纤维为模版,通过溶剂热法构建了p-CuO/n-In_2O_3异质结纳米纤维.采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法对所得材料的形貌和结构进行表征.结果表明,CuO纳米颗粒可以均匀地负载在超细In_2O_3纳米纤维表面;随着反应液中乙酸铜浓度的增加,负载的CuO纳米颗粒密度也逐渐增加.通过制备旁热式气敏器件对复合纳米纤维材料的气敏特性进行了研究.结果表明,与纯In_2O_3纳米纤维相比,p-CuO/n-In_2O_3异质结纳米纤维对H_2S气体具有较高的灵敏度和较低的工作温度.     

HYPERBRANCHED AROMATIC POLYMERS OBTAINED VIA SELF-CONDENSATION*

Hyperbranched aromatic polpmers were prepared by Friedel-Crafts reaction with Lewis acid, AlCl_3 and ZnCl_2, asthe catalysts. In this work, hyperbranched polybenzyl (PB) and poly(methylene) naphthalene(PN) were synthesized andcharacterized by ~1H-NMR and GPc. In addition, their florescence properties were measured with steady-state florescencespectra in THF and ethylene dichloride. The quantum yields of polybenzyl and poly(methylene)naphthalene in ethylenedichloride are much larger than those in THF.     

Size and composition control of Pt-In nanoparticles prepared by seed-mediated growth using bimetallic seeds

A two-step method has been developed for precise size and composition control of bimetallic Pt-In nanoparticles. Very small (1.62 nm) PtIn seed nanoparticles with 1:1 metal ratio were prepared in the absence of capping agents followed by growth of Pt on their surface in the presence of oleyl amine as reducing and stabilizing agent. Nanoparticles with bulk compositions of Pt(4)In, Pt(3)In, and Pt(2)In could be synthesized with average diameter smaller than 3 nm. TEM, EDX, and XPS provided evidence for homogeneous growth without separate nucleation of pure platinum nanoparticles in the reaction solution. Pt(3)In nanoparticles were deposited onto SiO(2) surface by incipient wetness impregnation. Temperature-induced changes in the particle surface were monitored by in situ IR spectroscopy and CO adsorption. It was found that surface alloy composition of the particles could be tuned by using oxidizing or reducing atmospheres.     

Mathematical algorithms applied to the multi-linear regression functions for the multicomponent determination of pharmaceutical dosage form containing three-component mixtures

In the presence of closely overlapping spectra, the quantitative multiresolution of ternary mixtures of three active compounds paracetamol (PAR), caffeine (CAF) and acetylsalycilic acid (ASP) in tablets, without using pretreatment such as separation step and graphical procedure of spectra was accomplished by the multivariate spectral calibration models, tri-linear regression calibration (TLRC), multi-linear regression calibration (MLRC) and Cramer's rule solution (CRS) of three linear equation functions in the matrix form. In the first two models, TLRC and MLRC are based on the use of the linear regression functions at selected wavelength sets in the spectral region of 210-300 nm. In the case of CRS model, A1(1) (1%, 1 cm) were used to obtain three linear equation functions and this linear equation system was resolved by the Cramer's rule for the prediction of PAR, CAF and ASP in samples. In the TLRC and CRS models, the selection of the appropriate wavelength set was performed by the Kaiser's technique. The algorithms of these mathematical calibration models were briefly described. The validation of TLRC, MLRC and CRS models was carried out by analyzing various synthetic ternary mixtures and by using the standard addition technique. These three calibration approaches were applied to the analysis of the real pharmaceutical tablets containing PAR, CAF and ASP. The obtained results were statistically compared with each other by using experimental and statistical tests. In the comparison of TLRC and MLRC models to the classical approach, CRS technique, the successful assay results were observed for the quantitative multiresolution of ternary mixture of the subject active compounds.