The productive scientific career of Charles Pedersen (October 3, 1904–October 26, 1989)

Charles Pedersen's career is reviewed from the time of his early life in Korea and Japan and scientific training in the United States to the present. His 42-year research career was practically and scientifically productive, leading finally to a share of the Nobel prize in chemistry for 1987. Commercially significant accomplishments included a large improvement in the yield of tetraethylead antiknock and discovery of the first oil soluble agents for inhibiting catalytic effects of copper in degradation of petroleum products and rubber. This led to a study of the interactions of metals with chelating agents and the resultant effects on oxidation reactions, thence to the behavior of peroxides and their reactions with substrates. He also discovered the antiknock activity of ferrocene. While studying the effects of ligands on the catalytic behavior of vanadium he discovered the crown compounds and their ability to include alkali metal ions. He devoted the last years of his career to elaborating their chemistry.Taken in part with permission fromCurrent Topics in Macrocyclic Chemistry in Japan, E. Kimura (ed.), Hiroshima University School of Medicine, Hiroshima, 1987.     

红外光谱计算分析鉴别海面溢油源的研究

本法将数字化的溢油和可疑溢油源样品的红外光谱视为N—维空间的两个矢量,它们间的角距离即作为定量比较两油品相似程度的依据。计算时选用表征油品组成特征的四个关键谱带:1600、1375、810和720cm~(-1)作为分析谱带。为了降低实验误差和风化影响,附加了一种新的数学处理过程,研究规划出N行M列(N>M)的线性矛盾方程组,用最小二乘解法处理原始数据求得问题的最可信赖解,从而用计算分析取得令人满意结果,并在现场执法服务中得到证实。     

在线式红外分光测油仪的校准

建立在线式红外分光测油仪的校准方法。在线式红外分光测油仪的校准主要包括绝缘电阻、示值误差、重复性、漂移和最小检出浓度等项目。通过分析实验数据,测量范围不大于10 mg/L时,示值误差不超过±0.8 mg/L;测量范围大于10 mg/L时,示值相对误差不超过±8%;重复性不大于2%;零点漂移不超过±0.5 mg/L,示值漂移不超过±5%;最小检出浓度不大于0.5 mg/L,仪器的计量性能正常。据此对影响仪器性能的各个参数进行全面评价,确认各项指标控制在合理范围内。该校准方法切实可行,可用于在线式红外分光测油仪的校准。     

Measurement of water by oven evaporation using a novel oven design. 2. Water in motor oils and motor oil additives

The measurement of water in lubricating oils is important because water accelerates the corrosion of metal parts and bearings in motors. Some of the additives added to lubricating oils to improve their performance react with the Karl Fischer reagent (KFR) causing a positive bias in the water measurement. A new oven evaporation technique for measuring water in oils has been developed that is automated, requires less sample handling, is easily calibrated, and is capable of measuring relatively small mass fractions of water (50 mg/kg sample). A series of motor oils was analyzed with the standard KFR, a reagent that detects interfering substances that reduce iodine, and the aldehyde–ketone reagent that does not detect substances that react with methanol and form water. The oil samples were heated to 107°C and then reheated to 160°C. At both temperatures, material was measured by both KFRs, but only zinc dithiophosphate released sulfur compounds that would react with the reagent that detects interfering substances. Mass fractions of between 20 and 70% of the volatile material released at either temperature were measured with the standard KFR but not with the aldehyde–ketone reagent. These results demonstrate that there are a number of sources of positive bias in the measurement of water in motor oils and that the standard KFR cannot be used to measure water in motor oils and motor oil additives. These results also indicate that some of the material reacts with methanol to form water. Finally, these results suggest that some of the material that is volatile at 160°C and not at 107°C may be water that is physically occluded or may be substances that react with diethyleneglycol monomethylether to produce water.     

茶叶和蔬菜中铅的同位素稀释电感耦合等离子体质谱的测定

采用同位素稀释电感耦合等离子体质谱(ID-ICP-MS)法测定了铅的含量,通过对茶叶标准物质(GBW-07605)中铅的测定,考察了方法的准确度和精密度,比较了同位素稀释法与普通外标定量法的测定结果。在5mLHNO3～0.5mLHF～1mLH2O2的消解体系中,ID-ICP-MS法测量茶叶中铅的回收率可达97.7%,相对标准偏差(RSD)小于1.2%。实验对市售的12种茶叶和10种蔬菜中Pb进行测定,铅含量符合相应国家标准的样品分别占总样品数的83%和90%。该法适合于植物样品中微量铅的测定。     

转换移动窗口因子分析法用于中药组合前后成分变化分析

以正十四烷为内标,采用气相色谱-质谱(GC/MS)联用技术对中药甘草(GUF)、甘遂(EKL)单味药材,以及其组成的药对(GUF-EKL)的挥发成分进行测定,基于一种新的化学计量学方法——转换移动窗口因子分析法(AMWFA)和直观推导式演进特征投影法(HELP)对产生的二维色谱/质谱数据同时进行分辨和解析,获取各个组分的纯色谱曲线和质谱,根据分辨得到的纯质谱在质谱库中进行相似检索以实现对组分的定性。利用AMWFA对组合前后的成分进行归属分析,然后采用面积归一法进行定量。分别在甘草、甘遂及其药对中鉴定出52、51和63个成分,占各自挥发油成分的84%、90%和75%。     

重质石油中含氮化合物的形态及分布分析──高效液相色谱－气相色谱在线联用分析方法研究

研究了高效液相色谱－气相色谱（ＨＰＬＣ－ＧＣ）联用技术及其应用。采用正相微柱ＨＰＬＣ－ＧＣ联用及完全溶剂蒸发方式，分析了煤焦油馏分──蒽油，显示了微柱ＨＰＬＣ－ＧＣ联用的应用潜力。采用正相ＨＰＬＣ－ＧＣ联用结合反冲技术，分离了重质石油中的饱和烃、芳烃和极性化合物（含氮化合物等）。     

川桂皮挥发油的化学组成

采用GC－MS技术分析了川桂（Cinnamomum wilsonii）皮挥发油的化学组成，共确定了其中42种化学成分与相对含量，占总组分相对含量的94．14％，其中有40种为萜类或其衍生物；研究结果显示，川桂皮油的主要成分为桉油素（11．02％），1（10），4－杜松二烯（10．21％），乙酸异龙脑酯（6．30％），杜松醇（5．53％），桉叶油醇（5．34％）等，与该植物叶和同属药用植物肉桂皮挥发油的主要组成均差别较大。     

大豆油树脂基泡沫塑料的力学性能与生物降解性研究

用丙烯酸酯化环氧大豆油(AESO)和甲基丙烯酸甲酯(MMA)经自由基共聚合制得一种新型的植物油基泡沫塑料.对AESO/MMA泡沫塑料的压缩性能的各种影响因素进行了细致研究,结果表明,所得泡沫塑料的压缩性能取决于AESO/MMA的比例、引发剂和促进剂的浓度.AESO泡沫塑料具有与传统不饱和聚酯泡沫塑料相似的压缩强度,而且比后者具有更高的韧性,同时这类植物油基泡沫塑料有着良好的生物降解性.     

高效液相色谱法测定印刷线路板热解油中的酚类化合物

建立了反相液相色谱法测定废旧印刷线路板热解油中的酚类化合物的方法,热解油经过滤并溶解在甲醇溶剂中可直接进样进行反相高效液相色谱分析,采用色谱柱为kromasil C18(4.6 mm i.d.×250 mm,5μm);流动相为乙腈/乙酸-乙酸铵缓冲溶液(0.01 mol/L,pH 4.0);柱温25℃;流速为1.0 mL/min,梯度洗脱进行分离,讨论了流动相的组成及其pH值等因素对组分分离产生的影响。实验结果显示,4种酚类化合物线性回归方程的相关系数r为0.9985~0.9996,高、中、低3个添加水平的加标回收率为96.3%~102.6%,相对标准偏差小于6%。