[Na(18-C-6)]2[Cu(i-mnt)2]的合成与结构分析

研究了18-冠-6与Na2[Cu(i-mnt)2][i-mnt=异丁二腈烯二硫醇阴离子,S2CC(CN)2-2]的反应,得到的配合物[Na(18-C-6)]2[Cu(i-mnt)2](1)通过元素分析、红外光谱、X射线单晶衍射进行了结构分析.配合物为单斜晶系,空间群P2(1)/c.晶体学结构数据a=1.2819(11),b=1.1793(10),c=1.4928(13)nm,β=99.121(16)°,V=2.228(3)nm3,Z=2,Dcaled.=1.369g/cm3,F(000)=958,R1=0.0521,wR2=0.1003.1中的[Cu(i-mnt)2]基团通过配体i-mnt的氮原子与两个[Na(18-C-6)]基团中的钠原子成键,形成稳定的中性配合物.     

Chromatographic characterization of high‐boiling petroleum fractions

Detailed investigation of solvent‐separated fractions of petroleum vacuum residues is necessary for understanding the separation mechanism using different solvents and to prepare better feedstocks for secondary conversion processes. The efficiency of different solvents to remove polars and insolubles from vacuum residues (of two Indian crude oils) has been studied. The solvents used were n‐heptane, n‐hexane, and n‐pentane (non‐polar) and ethyl acetate (polar). Soluble fractions were characterized for hydrocarbon group type analysis using high performance liquid chromatography (HPLC), average molecular weights using size exclusion chromatography (SEC), and boiling point distribution using high temperature gas chromatography (HTGC). Method development for HPLC analysis involved the study of parameters such as columns, solvent polarity, detectors, model compounds study, calibration, flow, and solvent gradient programming. The study demonstrated that ultimate soluble fractions have the least content of polar structures of the kind which can cause problems, during cracking and are least prone to cracking. The HPLC, SEC, and simulated distillation (SIMDIS) methods developed and standardized are simple, accurate, and suitable for the rapid assay needed for quick compositional surveys.     

Internal standardization for the determination of cadmium,cobalt, chromium and manganese in saline produced water from petroleum industry by inductively coupled plasma optical emission spectrometry after cloud point extraction

In the present paper a procedure is proposed for the determination of traces of Cd, Co, Mn and Cr in petroleum industry produced water by inductively coupled plasma optical emission spectrometry. The procedure is based on cloud point extraction of these metals, as their dithizonate complexes, into the surfactant-rich phase of octylphenoxypolyethoxyethanol surfactant (Triton X-114). Extractions were carried out in solutions with salinities between 10‰ and 70‰. Since residual salinity in the surfactant-rich phase caused differences in its transport to the plasma, yttrium was used as an internal standard to correct for this effect. The simultaneous metal extraction procedure was optimized by response surface methodology using a Doehlert design and desirability function. Enhancement factors of 21, 21, 9 and 19, along with limits of quantification of 0.093, 0.20, 0.73 and 1.2 μg L^− 1, and precision expressed as relative standard deviation (n = 8, 20.0 μg L^− 1) of 5.8, 1.2, 1.7 and 5.7% were obtained for Cd, Co, Mn and Cr, respectively. The accuracy was evaluated by spike recovery tests on the high salinity water samples with salinity of 40 and 63‰.     

1-甲基环氧乙烷-1-丙炔醚的结构测定及其核磁图谱

以¹H-NMR谱和¹³C双自旋回波的APT脉冲序列测定文献中尚未曾发表的化合物HC≡C-CH₂-O-C^CH₃-_O-CH₂文中计算了峰强度与脉冲间隔时间的关系,讨论了各谱线的相位并区分出-CH₃、-CH₂、-CH和季碳。     

Imaging of wood tissue by ToF-SIMS: Critical evaluation and development of sample preparation techniques

Tissue of Norway spruce wood was investigated by time-of-flight secondary-ion mass spectrometry (ToF-SIMS) and field-emission scanning electron microscopy (FE-SEM). Different sample preparation techniques (including sectioning and drying) traditionally used for SEM analysis were compared and critically evaluated. A high contamination of wood surfaces by polytetrafluoroethylene (PTFE) introduced onto the sample during sectioning was detected by ToF-SIMS. A new protocol was developed and images of wood sections dried in different ways were compared. Main location of Mg, Na, K and Ca, but no lignin in membranes of bordered pits in spruce section surfaces was detected by ToF-SIMS imaging if critical point drying (CPD) or acetone extraction followed by drying under nitrogen flow (AEND) was applied. No specific locations of wood components as well as low signals from metal ions (Mg and Na) were observed on the wood surfaces of freeze-dried (FD) or air-dried (AD) sections. It was found that extractive substances, presenting on surfaces of FD and AD wood section, were evenly distributed on the surfaces and interfered with ToF-SIMS analysis. Our results indicated that ToF-SIMS imaging was critically sensitive to the sample preparation technique and a strict protocol for characterization of metals, lignin and polysaccharides in wood was suggested.     

高强度高电导率聚乙炔的合成——醚类溶剂的结构对性能的影响

通过选用不同醚类结构做溶剂加热回流Ti(OBu)_4-AIEt_3催化剂,并采用非溶剂聚合方法进行乙炔聚合发现,所得HPPA膜的强度和电导率都有了较大提高。其中直链醚制得的PA膜强度(抗张强度大于100MPa)和空气稳定性比用环醚得到的PA膜高得多,但用前者时的乙炔聚合速率远低于后者。两体系得到的HPPA膜的碘掺杂电导率值相近(～10~3S/cm),拉伸后可达10~4S/cm量级。SEM、TEM及IR光谱的结果表明,不同醚制得的PA膜的纤维束直径及顺式含量有较大差别。     

含嘧啶环的双冠醚(Ⅳ)

前文已报道由啶环桥联两个苯并冠醚的双冠醚的合成与性质。由于嘧啶环的刚性较大,能把两个冠醚单元固定在有效地协同作用位置,因此以它们作中性载体的离子选择性电极具有较好的选择性。为了进一步研究这类双冠醚的性质,我们合成了四种嘧啶环桥联两个脂肪族冠醚的双冠醚,并经元素分析、IR、′HNMR鉴定。     

Supercritical fluid chromatography of petroleum products using flameless sulfur chemiluminescence detection

Supercritical fluid chromatography using flameless sulfur chemiluminescence detection has been investigated for the analysis of sulfur compounds in petroleum products. The chromatography and detection system was easy to implement and exhibited good precision, linearity, selectivity, and sensitivity. A minimum detectable limit of 0.3 pg sulfur/s was obtained, and response to sulfur in different sulfur species was nearly equimolar.     

LAH aryl alkyl ether cleavage of BINOL derivatives

Herein we report the cleaving of aryl alkyl ethers on BINOL derivatives, using the common reducing agent LAH. The cleavage of the alkyl oxygen bond is observed when the BINOL derivative is treated with LAH, in refluxing dioxane, for 60 h. The resulting BINOL derivative can then be re-alkylated using a standard Williamson ether synthesis. The same procedure was tested on 6-hydroxy-2-naphthoic acid derivatives and cleavage was not observed, thus suggesting a chelating mechanism for the BINOL ether cleavage.     

Determination of hopane biomarkers in Arabian crude oils by gas chromatography-tandem mass spectrometry

Gas chromatography-mass spectrometry with the mass spectrometer operated in the tandem mode at a constant accelerating voltage was used to analyse for triterpanes in Arabian crude oils. Specific molecular parent-daughter ion pairs were selected for quantitative measurements owing to their metastable transitions in the first field-free region. More accurate relative distribution ratios of hydrocarbon biomarkers were determined by this sequential gating technique than by the conventional diagnostic daughter ion mass fragmentogram in common GC-MS. The data and spectra obtained from MS-MS operation may serve as unique “fingerprints” for these regional crudes