三烷基氧化膦辐照分解气态烃类的气相色谱测定

报告了萃取剂三烷基氧化膦在γ射线辐下分解产生的气态烃类的气相色谱分析法。测定了甲烷、乙烷、乙烯、丙烷和丙烯。采用预空取样,ＧＤＸ１０２充柱,氢火焰离子化检测器。方法简便、快速,用此法测定了辐照剂量１０＾４～１０＾６Ｇｙ的三烷基氧化膦样品,获得满意结果。     

有机磷化合物的研究 ⅠⅣ.合成烷基膦酸单酯衍生物的新方法

Atherton与Todd等1945年就用亚磷酸二烷基酯在四氯化碳中与有机胺反应得到二烷基磷酰胺.我们曾成功地由二烷基亚磷(膦)酸在四氯化碳存在下与多种亲核试剂反应合成二烷基磷(膦)酸酯及其衍生物.实验表明二烷基亚膦酸的反应性和亚磷酸二烷基酯有很大差别,为进一步考察不同的三配位磷化合物在该反应中的反应性能,我们合成了己基亚膦酸单烷基酯并在四氯化碳中与各种亲核试剂进行氧化膦酰化反应,制得了相应的己基膦酸单酯衍生物,得率良好,为合成烷基膦酸单酯衍生物的新方法.     

烷基磷(膦)酸酯~(31)P NMR的取代基效应

本文利用分子力学计算,将核磁共振中烷基取代基效应的Van der Waal模型扩展到磷酸三烷基酯、烷基膦破二烷基酯、二烷基膦酸烷基酯和三烷基氧化膦。在各类磷化合物中,δ~(31)P和E_(vdw·p)之间存在有良好线性关系。此外,还用分子力学计算方法和变温核磁共振谱方法探讨了一系列烷基膦酸O,O-1,3-亚丙酯和烷基膦酸O,O-1,4-亚丁酯的构型平衡。在气相和非极性溶剂中,前者以烷基处于平键的椅式构型存在,后者以烷基处于平键的扭船式构型存在。     

相转移催化合成苯基烷氧羰基甲基次膦酸酯和二苯基烷氧羰基甲基氧化叔膦

液-液相转移催化 P-烷基化反应的研究工作还不多。Kem 等曾用亚磷酸二烷基酯或二烷基氧化膦与氯代的取代乙酰胺通过液-液相转移法合成了取代胺基羰基与甲基膦酸酯及氧化叔膦。我们曾研究了亚膦酸二烷基酯与氯     

有机磷聚合物的合成——Ⅱ.聚2,2’-[二对次苯基烷(苯)基氧膦]-5,5’-联苯并咪唑

1.用双(对羧苯基)烷基(或苯基)氧膦与3,3’-二氨基联苯胺缩聚,合成了三个在主链上带有联苯并咪唑和氧化三烃基膦结构的高分子化合物。初步研究了这类含磷高聚物的 热稳定性和化学稳定性及其红外光谱。 2.合成了两个文献上未报导过的含磷化合物——双(对甲苯基)正丁基氧膦和双(对羧苯基)正丁基氧膦。     

有机磷化合物的研究(LVII)——二苯(氧)基氯膦对肟基的自由基加成——合成1-氨基取代三烷基氧化膦及烷基膦酸酯的新途径

二苯基氯膦或二苯氧基氯膦对醛(酮)肟的反应可作为合成1-氨基烷基二苯基氧化膦或1-氨基烷基膦酸二苯酯的新方法,具有条件温和、操作方便及得率高的优点。EPR研究结果揭示了这类反应属自由基机理。     

Pd催化交叉偶联P-C键形成反应

近30年来,Pd催化交叉偶联形成P-C键的反应在药物、催化剂配体、阻燃剂和高分子材料等领域受到普遍重视。本文介绍了Pd催化交叉偶联反应形成P-C键的方法,以及利用该法制备有机膦化合物的研究进展。作为反应底物的磷亲核试剂包括亚磷酸二烷基酯、亚膦酸酯、次膦酸酯、氧化膦、伯或仲膦、三芳基膦、亚磷酸三烷基酯、膦-硅(锡)化合物和膦-硼烷复合物等,参与偶联反应的亲电试剂包括卤代烯烃、卤代芳烃、三氟甲磺酸烯基酯、三氟甲磺酸芳基酯、乙烯基硼酸酯等,并对反应机理、反应条件和反应的影响因素进行了探讨。     

三烷基氧化乙烯基硅烷的合成

本文报告用过苯甲酸(按照Прилежаев方法)将三烷基乙烯基硅烷中的双键氧化,结果制得两种新化合物,即三甲基氧化乙烯基硅烷和三乙基氧化乙烯基硅烷,产率分别为69％和72％,是具有樟脑气味的透明液体。     

烷基膦酸单酯的合成

用烷基膦酸二酯催化水解合成了相应的酸性单酯。首次建立了用叔丁基氯制成的Grignard试剂与亚磷酸二酯反应、继而用Todd碱性氧化法合成高位阻叔丁基膦酸单酯的新的合成路线, 这一合成路线比用Clay反应、继而醇解和水解的方法得率高。     

顶空气相色谱法测定γ辐照三烷基氧膦中轻质烃

研究了用气相色谱法测定经γ辐照三烷基氧膦(TRPO)中的轻质烃。对实验条件进行了优化。结果表明，此方法可检测TRPO中已烷—癸烷，各组分回收率为90％一108％，RSD为2．7％一9．0％。     

离子交换净化辐照三烷基氧化膦中脂肪酸

本文研究了用大孔阴离子交换树脂D301R从乏萃取剂30%TRPO-煤油溶液中净化去除脂肪酸的方法,探讨了该法用于乏萃取剂净化的可行性。     

Simultaneous determination of amounts of major phospholipid classes and their fatty acid composition in erythrocyte membranes using high-performance liquid chromatography and gas chromatography.

A method for the simultaneous determination of amounts of major phospholipid classes and their fatty acid composition in erythrocyte membranes is described. The method consists in extraction of phospholipids from erythrocyte membranes, separation of phospholipid classes by high-performance liquid chromatography, methylation of phospholipids and determination of phospholipid-bound fatty acids by capillary gas chromatography. The amounts of phospholipid classes are calculated from the total weight of phospholipid-bound fatty acids and their average molecular weights. The method was applied to erythrocytes from rats. The results show that the method is reproducible and is useful for the determination of amounts of phospholipid classes and their fatty acid composition in small blood samples.     

树脂酸性组分的氢氧化四甲铵甲基化与GC-MS分析

利用氢氧化四甲铵(TMAH)对马尾松树脂(塔罗油)进行甲基化，并对其产物进行GC—MS分析；研究表明TMAH甲基化后进行GC—MS分析是测定树脂中酸性组分的一种快速有效的方法，但酸性组分中的脂肪酸要比树脂酸难于甲基化，因此为了确保甲基化反应完全，应适当延长甲基化反应时间。     

Measurement of oleic acid in human plasma by isotope dilution mass spectrometry

Summary A method for the quantitative determination of oleic acid in human plasma by isotope-dilution mass spectrometric technique is described. For the measurement of the fatty acid concentration (1-¹³C) oleic acid is added to the plasma sample. The fatty acids are extracted with n-hexane. Portions of the extract are esterified by the boron trifluoridemethanol method or stable isotope methylation. The methyl ester derivatives of the fatty acids are separated and detected by GC-MS with the mass spectrometer set to m/z 296 and 297. For the measurement of oleic acid after stable isotope methylation the m/z 299 and m/z 300 are monitored. The amounts of oleic acid in the plasma are calculated from the isotope ratios measured by selected ion monitoring. The recovery of the methylation step and the precision and accuracy of the GC-MS method are presented and discussed.     

超临界CO_2萃取-气相色谱质谱法测定斑点叉尾鮰肌肉中的脂肪酸

采用超临界CO2萃取工艺、气相色谱-电子电离质谱(GC-EI-MS)法,建立了斑点叉尾鮰肌肉中脂肪酸的定性与定量分析方法。在CO2流速为30 L/h、温度45℃、压力25 MPa、时间100 min条件下进行超临界CO2萃取,所得油脂皂化10 min,采用三氟化硼法进行甲酯化衍生20 min,经HP-Innowax毛细管柱分离,电子电离质谱检测,以全扫描模式定性分析,选择离子扫描模式定量分析,饱和脂肪酸、单不饱和脂肪酸、双不饱和脂肪酸、多不饱和脂肪酸的定量离子分别为m/z74,55,67和79。14种脂肪酸甲酯的检出限和定量限分别在2.2～20μg/L和7.4～60μg/L之间;平均回收率为90.0%～111.2%,相对标准偏差为2.0%～5.9%。本方法灵敏度高、重复性好,可用于测定斑点叉尾鮰肌肉样品的脂肪酸。     

Rapid Analysis of Fatty Acid Composition in Polysorbate 80 by Gas Chromatography with On-line Pyrolytic Methylation Technique

A novel method of on-line pyrolytic methylation–gas chromatography was developed for the rapid analysis of fatty acid composition in Polysorbate 80 without any tedious pre-treatment steps. Fatty acids in Polysorbate 80 were converted into their corresponding fatty acid methyl esters in the presence of trimethylsulfonium hydroxide with a vertical microfurnace pyrolyzer at 300 °C. The premixing procedure of sample and organic alkali reagent was necessary before the on-line pyrolytic methylation to improve the repeatability. The relative standard deviations for peak areas of fatty acids in Polysorbate 80 were over the range of 0.3–9.1% (n = 5). Six Polysorbate 80 samples, consisting of three samples of pharmaceutical grade and three samples of non-pharmaceutical grade, were analyzed to evaluate the feasibility of the proposed method. The relative percentages (%) of fatty acids for samples of pharmaceutical grade meet the Chinese Pharmacopoeia requirements with the amount of oleic acid varying from 78.4 to 89.3%. On the other hand, the relative percentages (%) for palmitic acid and stearic acid in samples of non-pharmaceutical grade were out of the specification limits, with the amount of oleic acid varying from 62.0 to 63.5%. The quantitative results determined by on-line pyrolytic methylation were in agreement with those obtained by off-line methylation. The result proved that gas chromatography with on-line pyrolytic methylation technique is of great value for rapid screening analysis of Polysorbate 80 samples in bulks.     

Determination of fat content and fatty acid composition in meat and meat products after supercritical fluid extraction

Two different relatively simple, commercially available supercritical fluid extractors (SFE), Leco and Foss-Tecator, were tested for the determination of total fat content in meat and meat products. The fatty acid composition in meat and meat products was also determined after the Foss-Tecator extraction in an aliquot of the extract. Total fat was determined by weighing after the different extraction procedures and the fatty acid composition by gas chromatography after hydrolysis and methylation of the extract. The results for total fat content agreed well with results from a standard method of Schmid, Bondzynski, and Ratzlaff, which uses conventional solvent extraction. Fatty acid composition was compared with the Bligh and Dyer extraction, and showed good agreement. The average relative difference between SFE and Bligh and Dyer of all fatty acids in the sample was <3% for acids exceeding 0.5% of total fatty acid amount. The advantages of SFE over traditional methods are a much lower consumption of hazardous organic solvents and shorter extraction times. To obtain quantitative recoveries by SFE, ethanol was added to the extraction cells before extraction.     

植物油的质谱分析：1.蓖麻油

运用一种植物油的系统分析方法测定蓖麻油的精细组分，这包括皂化，ＢＦ３－ＭｅＯＨ甲基化，ＧＣ－ＣＩＭＳ法测定脂肪酸碳链长度和不饱和度，ＡＭＰ衍生化，ＧＣ－ＥＩＭＳ测定不饱和脂肪酸的双链位置，分析了蓖麻油的十一种脂肪酸组分，有五个为未知组分，并测定了其中三个组分的双链位置。     

Gas chromatographic/mass spectrometric analysis of the essential oil of Houttuynia cordata Thunb by using on-column methylation with tetramethylammonium acetate

This paper describes a simple and novel on-column derivatization procedure used with gas chromatography/mass spectrometry (GC/MS) for the analysis of essential oil of Houttuynia cordata Thunb (HCT), a traditional Chinese medicine. In the procedure, the essential oil was obtained by hydrodistillation, and the fatty acid components were derivatized with tetramethylammonium acetate (TMAA) at 250 degrees C and identified by GC/MS. Methylation improved the determination of both the fatty acids and the other components in the essential oil of HCT. To obtain optimum methylation conditions, several important factors were investigated with pentadecane as the internal standard and a GC inlet temperature of 250 degres C. Tetramethylammonium hydroxide (TMAH) and TMAA were compared as the derivatization agent, and a 2:1 ratio of TMAA to capric acid was evaluated. Fatty acid methyl esters produced good chromatographic peak shapes and did not interfere with the determination of dodecanal and caryophyllene. TMAA is a neutral methylation reagent, and it yielded no side reactions during derivatization. It was found that the fatty acid content of the essential oil was about 81%; among the methylated fatty acids found were capric acid, methyl (43.66%), methyl laurate (16.15%), methyl hexadecanoate (9.27%), undecanoic acid, methyl (5.62%), methyl oleate (1.98%), and methyl linoleate (1.40%). Other major constituents were (-)-beta-pinene (1.02%), beta-myrcene (1.62%), 1-terpinen-4-ol (1.59%), decanal (1.49%), and 2-undecanone (1.47%). The results obtained demonstrated good efficiency for the procedure. Pure chromatograms allowed quantitation, which was obtained by total volume integration. The on-column derivatization procedure was simple to perform, and it improved the sensitivity, the peak resolution, and the selectivity of the GC/MS determination.     

血清总磷脂脂肪酸组分的固相萃取-气相色谱法分析

以硅胶基质为固定相,建立了固相萃取-气相色谱(SPE-GC)分离检测血清总磷脂中脂肪酸含量的方法。优化了SPE的洗脱方式及甲醇洗脱量,探讨了衍生化步骤的优化条件。该法对磷脂中各脂肪酸组分测定的线性相关系数约为0.999,回收率在80%左右;日内误差小于4.8%,日间误差小于8.9%。用固相萃取柱分离磷脂简单、快速、有效,用气相色谱检测磷脂中脂肪酸组分方法稳定、可靠。