环氧氯丙烷作重原子微扰剂在环糊精诱导室温磷光法中的应用

本文报道一种新型的重原子微扰剂－环氧氯丙烷（ＥＣＨ）,在此重原子微扰下,建立了β－环糊精诱导室温磷光法（β－ＣＤ－ＲＴＰ）测定痕量溴代萘（ＢｒＮ）的方法,结果令人满意。同时还在该体系中测定了溴代萘的ＤＴＰ寿命、猝灭常数、三元包合物的包接常数。实验结果证明,α－ＢｒＮ／ＥＣＨ／β－ＣＤ三分子包接配合物比β－ＢｒＨ／ＥＣＨ／β－ＣＤ三分子包接络合物包接更加有效,而且稳定性更强。     

邻氨基酚-过氧化氢-辣根过氧化物酶伏安酶联免疫分析法测定人血清甲胎蛋白

提出了邻氨基酚（ＯＡＰ）－Ｈ２Ｏ２－辣根过氧化物酶（ＨＲＰ）伏安酶联免疫分析法测定人血清甲胎蛋白（α－ＦＰ）的新方法．该方法是将ＨＲＰ催化Ｈ２Ｏ２氧化邻氨基酸的酶催化反应与邻氨基酚的氧化产物在滴汞电极上的还原反应相偶合，在ＢＲ缓冲溶液中，在－０．４３ Ｖ（ｖｓ．ＳＣＥ）左右产生灵敏的极谱波．根据测定标记在甲胎蛋白抗体上的ＨＲＰ的量，求得发生免疫反应的 α－ＦＰ的含量。该方法对甲胎蛋白测定的线性范围为 １． ２５～４００ ｍｇ／Ｌ。用所建立的方法对病人血清样品进行了测定，并与酶联免疫吸附测定光度法（ＥＬＩＳＡ）进行对照，二者相关性很好。     

水合希土硝酸盐与本并及单环己基-12-冠-4配合物的合成、性质及晶体结构

在乙腈介质中合成了苯并－１２－冠－４（简称Ｂ－１２－Ｃ－４）和单环己基－１２－冠－４（简称Ｃｙ－１２－Ｃ－４）的六种希土配合物：ＲＥ（ＮＯ３）３·Ｂ－１２－Ｃ－４（ＲＥ＝Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ），ＲＥ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４（ＲＥ＝Ｌａ，Ｌｕ）。研究了它们的ＩＲ及＾１ＨＮＭＲ性质，并测定了四种单晶的结构，用ＩＮＤＯ法计算了Ｌｕ（ＮＯ３）３·Ｂ－１２－Ｃ－４，Ｌｕ（ＮＯ３）３·Ｃｙ－１２－Ｃ     

反相离子对高效液相色谱法测定动物血浆中的恩诺沙星及其代谢物

 建立了用反相离子对ＨＰＬＣ测定动物血浆中恩诺沙星（ＥＲＦＸ）及其代谢产物环丙沙星（ＣＰＦＸ）浓度的方法。血浆中药物用二氯甲烷萃取，选用ＯＤＳ柱，甲醇－四丁基氢氧化铵溶液为流动相，吡哌酸（ＰＰＡ）作内标，检测波长２７２ｎｍ。方法简便、快速、灵敏、准确，适用于ＥＲＦＸ及其代谢物ＣＰＦＸ血药浓度的测定和药代动力学研究。并首次测定了黄牛血浆中的ＥＲＦＸ和ＣＰＦＸ。     

邻联甲苯胺-过氧化氢催化光度法测定钴

１引言 在碱性介质中,痕量Ｃｏ（Ⅱ）见对Ｈ２Ｑ２氧化邻联甲苯胺（ｏ－Ｔｏｌｉｄｉｎｅ）的显色反应具有强烈的催化作用,探讨了利用该反应进行痕量Ｃｏ（Ⅱ）测定的影响因素,建立了测定痕量Ｃｏ（Ⅱ）的催化动力学光度法,该方法的灵敏度为１．７８ × １０－６ｇ／Ｌ,测定的线性范围为０．８～３．６ μｇ／Ｌ Ｃｏ２＋,应用于维生素Ｂ１２中痕量Ｃｏ（Ⅱ）的测定,结果满意。２实验部分２．１仪器与试剂 ７２１－１００型分光光度计;电热恒温水浴槽;Ｎｉｃｏｌｅｔ ＦＴ－ＩＲ ５ＤＸ红外光谱仪。钴（Ⅱ）标准溶液：１ｍｇ／Ｌ;…     

离子交换/8-羟基喹啉荧光法分别测定天然水中的无机和有机单核铝

采用离子交换／氯仿萃取－８－羟基喹啉荧光法（８－Ｏｘ－ＣＦ－ＥＦ）分别测定了天然水样中的无机和有机单核铝。与Ｄｒｉｓｃｏｌｌ建立的铝形态区分法进行了比较,结果一致,本法优点是：可以直接测定水中的无机单核铝,减少了实验误差。     

水溶性[5-邻(乙氧羰基甲氧基苯基)-10,15,20-Tri(4-N-甲基吡啶基)]卟啉铜(Ⅱ)配合物的合成、表征及其和单核苷酸的相互作用

合成并表征了「５－ｏ（乙氧羰基甲氧基苯基）－１０,１５,２０－Ｔｒｉ（４－Ｎ－甲基吡啶基」卟啉Ｈ２「５－ｏ－（Ｅｍｏｐｈ）－Ｔｒｉ（４－Ｎ－Ｍｅｐｙ）」ＰＰ（１）及其铜配合物Ｃｕ「５－ｏ－（Ｅｍｏｐｈ）－Ｔｒｉ（４－Ｎ－Ｍｅｐｙ）」ＰＰ（２）,用紫外－可见光谱滴定法测定配合物（２）与单核苷酸的配位平衡常数,研究了它作为主体分子和单核苷酸的相互作用。研究结果表明,各配体结合常数按Ｋ（ｄＧＭＰ）〉Ｋ（ｄＡＭＰ）〉Ｋ（ｄＴＭＰ）〉Ｋ（ｄＣＭＰ）≥Ｋ（ｄＵＭＰ）的顺序依次减小。测定了π－π配合反应的△,Ｇ,△ｒＨ,△ｒＳ,发现该反应是放热,熵减小的过程,该反就体系存在焓熵补偿关系。     

OARP—H2O2—HRP伏安酶联免疫分析新体系测定人血清甲胎蛋白

本文提出邻氨基酚（ＯＡＰ－Ｈ２Ｏ２－辣根过氧化物酶（ＨＲＰ）伏安酶联免疫分析体系并用于人血清中甲胎蛋白（αＦＰ）的测定。该方法是将ＨＲＰ催化Ｈ２Ｏ２氧化ＯＡＰ的酶催化反应与邻氨基酚的氧化中间产物（邻苯醌亚胺）在滴汞电极上的还原反应相偶合,在ＢＲ缓冲溶液中,在－０．８７Ｖ（ｖｓ,ＳＣＥ）左右产生灵敏的极谱波。根据测定标记在甲胎蛋白抗体上的ＨＲＰ的量,求得发生免疫反应的αＦＰ的含量。这该方法对甲胎蛋白测定的线性范围为１．２５－４００ｍｇ／Ｌ。用所建立的方法对病人的血清样品进行了测定,并与酶联免疫吸附测定光度法（ＥＬＩＳＡ）进行对照,二者相关性很好。     

离子对反相色谱法研究（E）－4，4′－二氨基二苯乙烯－2，2′－二磺酸及其杂质组分

建立了离子对反相ＨＰＬＣ分离测定（Ｅ）－４，４′－二氨基二苯乙烯－２，２′二磺酸［（Ｅ）ＤＡＳ］及其中间产物和杂质组分的方法。解决了测定的稳定性问题，且各组分线性范围宽，检测限低。已用于工业样品的测定，结果令人满意。     

二苯并18－冠－6辅助钡离子在1，2－二氯乙烷／水微界面转移的伏安研究

应用液／液界面微电极对二苯并１８－冠－６（ＤＢ１８－Ｃ－６）辅助推动Ｂａ~（２＋）在１，２－二氯乙烷／水（ＤＣＥ／Ｗ）界面转移的电化学过程进行了详细探讨，证明该过程遵循ＴＩＣ机理，是受扩散控制的可逆过程。通过转移电流和反应物浓度之间的线性关系，测定了Ｂａ~（２＋）以及用其它方法难以测定的ＤＢ１８－Ｃ－６。     

棒状薄层色谱/氢火焰离子化检测器复杂混峰谱图特征提取方法的研究及应用

分析了各种工艺的重油样品近300种，通过各样品的薄层色谱图提取了谱图识别的特征变量，实现了由TLC／FID谱图识别样品类型的目的，并采用偏最小二乘方法将谱图数据特征与洗脱色谱法（eluting chromatography，简称EC^[2]法）进行了关联，从而用于重油样品的烃族组成分析，预测结果与EC法相符。     

Structural characterization of ethyl cellulose and its use for preparing polymers with viologen moieties

The characteristics of ethyl cellulose (EC) were studied by chemical reaction and the spectra method. EC was first tosylated with tosyl chloride, and then the tosylated EC (Ts-EC) reacted with sodium iodide (NaI). By comparing the NMR spectra of EC and iodine-substituted EC (EC-I), a free hydroxyl group was proved to exist at the C-6 of the D-glucose unit of cellulose. Viologen moieties were introduced into the EC chain by the reaction of Ts-EC with 4,4′-bipyridine and n-propyl bromide. The existence of viologen was confirmed by ¹H-NMR, IR, and ESR. © 1993 John Wiley & Sons, Inc.     

Analysis of the release process of phenylpropanolamine hydrochloride from ethylcellulose matrix granules IV.(1)) Evaluation of the controlled release properties for in vivo and in vitro release systems

In the pharmaceutical preparation of a controlled release drug, it is very important and necessary to understand the release properties. The dissolution test is a very important and useful method for understanding and predicting drug-release properties. It was readily confirmed in the previous paper that the release process could be assessed quantitatively by a combination of the square-root time law and cube-root law equations for ethylcellulose (EC) matrix granules of phenylpropanolamine hydrochloride (PPA). In this paper EC layered granules were used in addition to EC matrix. The relationship between release property and the concentration of PPA in plasma after administration using beagle dogs were examined. Then it was confirmed that the correlativity for EC layered granules and EC matrix were similar each other. Therefore, it was considered that the dissolution test is useful for prediction of changes in concentration of PPA in the blood with time. And it was suggested that EC layered granules were suitable as a controlled release system as well as EC matrix.     

Estimation of Ethyl Cellulose Layer Thickness of Coated Polyethylene Oxide Particles Using Differential Scanning Calorimetry

Particles of poly(ethylene oxide) (PEO) were coated using ethyl cellulose (EC). Equations and a method were proposed to estimate the EC layer thickness by using differential scanning calorimetry (DSC) based on melting or crystallization heat of phase-change materials. The result shows that EC layer thickness of polyethylene oxide particles determined using DSC is consistent with the result using an optical microscope.     

Multiple headspace solid-phase microextraction of ethyl carbamate from different alcoholic beverages employing drying agent based matrix modification

Multiple headspace solid-phase microextraction (MHS-SPME) combined with gas chromatography-nitrogen phosphorus detector is proposed to determine the toxic contaminant ethyl carbamate (EC) in various alcoholic beverages after matrix modification. The remarkable feature of this method is that matrix effect, which commonly appears in SPME-based analysis, is avoided by determining the total amount of the analyte in the sample. To increase the sensitivity of the method, a novel polyethylene glycol/hydroxy-terminated silicone oil fiber was developed by sol-gel technique and applied for the analysis. Owing to the high polarity and hydrophilia of EC, an important problem still remains because the adsorption by sample matrix causes low transport of EC to the headspace and thus invalidates MHS-SPME for quantification. Mixing with anhydrous sodium sulphate, the sensitivity of the method can be improved. A Taguchi's L(16) (4(5)) orthogonal array design was employed to evaluate potentially significant factors and screen the optimum conditions for MHS-SPME of EC. Under the optimized conditions, limit of detection of 0.034 mg L(-1) was obtained. Relative standard deviation of replicate samples (n=6) was 2.19%. The proposed method was linear in the range of 0.04-100 mg L(-1), and the coefficient of determination was 0.9997. The method was used to determine EC in various alcoholic beverages. The concentrations obtained were compared with those obtained by standard addition method and no statistically significant differences were observed.     

酒精度对高效液相色谱-荧光法分析白酒中氨基甲酸乙酯含量的影响

分析酒精度对高效液相色谱-荧光（HPLC-FLD）法测定白酒中氨基甲酸乙酯（EC）含量的影响,建立了快速检测白酒中EC含量的HPLC-FLD分析方法。通过比较不同酒精度下同一EC含量的峰面积,研究酒精度对EC含量测定的影响。结果表明,在5%~65%（v/v）酒精度范围内,酒精度与EC含量（峰面积）具有良好的线性关系,相关系数R²大于0.98,同时建立了不同酒精度间EC含量换算的相对校正系数。该方法在10~500 μg/L范围内呈良好的线性关系,R²大于0.9999,定量限为10 μg/L,加标回收率为98.9%~108.2%,相对标准偏差为0.6%~4.9%。评价了HPLC-FLD法的可靠性,将该方法与GC-MS方法比较,结果显示两种方法无明显差异。该方法简单、灵敏、准确,适用于白酒中EC含量的快速测定,具有较好的实际应用价值。     

Preparation of a fluorescent derivative of benzoylecgonine, and preliminary studies of its application to the analysis of urine.

A sensitive high-performance liquid chromatographic method using 3-bromomethyl-6,7-dimethoxy-1-methyl-2(1H)-quinoxalinone (Br-DMEQ) as a fluorescent labeling reagent is described for the determination of benzoylecgonine (BE) and ecgonine (EC). The Br-DMEQ derivatives of BE and EC were separated on a C18 column and detected at 455 nm with excitation at 370 nm. The detection limits of the proposed method were 18.7 fmol for BE and 12.5 pmol for EC at a signal-to-noise ratio of 3. Relative standard deviations of five replicate measurements were 1.94% (10 pmol) and 2.98% (50 pmol) for BE and 6.3% (250 pmol) and 5.62% (1.25 pmol) for EC. This method was applied to the determination of BE in human urine. BE was extracted from urine by solvent extraction with chloroform-isopropyl alcohol (9:1, v/v) solution. Levels of 2.5.10(-8) M BE in urine (25 pmol/ml) could be determined.     

Determination of acetochlor in technical and formulated products by capillary gas chromatography: PVM 5:1999

A peer-verified gas chromatographic (GC) method is presented for the weight percent (wt %) determination of acetochlor herbicide in technical and formulated products. During method development, the method was found to be rugged by the Youden Ruggedness Test. Two laboratories with experience in the wt % determination of acetochlor in various matrixes participated in this study. Each laboratory received 10 blind duplicate test samples of the following 5 matrixes: one acetochlor technical and 4, different, emulsifiable concentrate (EC) formulations--Harness EC (MON 5841), Harness Export/Fist (MON 8435), Surpass EC (HF), and Surpass EC (LF). Each participant was asked to make duplicate weighings of each of the test samples and to inject each test sample solution twice. All test samples were analyzed on the same day, and 8 data points (replicates) per matrix were obtained. The test samples were dissolved in acetone that contained dipentyl phthalate as an internal standard. They were analyzed by GC on a 15 m capillary column by using split injection and a flame ionization detector. Acetochlor (wt %) was determined by comparing the ratios of peak area of acetochlor/peak area of dipentyl phthalate internal standard obtained for the test sample and calibration solutions. Repeatability of the method, expressed as the within-laboratory (between replicates) relative standard deviation (RSDr), was found to be 0.09-0.77% for the 5 matrixes. Reproducibility of the method, expressed as the within-test sample relative standard deviation (RSDR), was found to be 0.18-0.78% for the     

Application of positive ion chemical ionisation and tandem mass spectrometry combined with gas chromatography to the trace level analysis of ethyl carbamate in bread

A rapid, sensitive and selective method has been developed and validated for the analysis of the contaminant ethyl carbamate (EC) in bread products at the part-per-billion level. The new procedure uses positive ion chemical ionisation (PICI) and tandem mass spectrometry (MS/MS), combined with gas chromatography (GC), on a 'bench-top' triple-quadrupole mass spectrometer. Ammonia was the PICI reagent gas of choice because of its ability to produce abundant [M+H]+ and [M+NH4]+ ions from EC and deuterium-labelled EC (LEC) used as an internal standard. For identification and quantification, selected reaction monitoring (SRM) was used to follow the precursor-to-product ion transitions of m/z 107 --> 90, m/z 107 --> 62 and m/z 90 --> 62 for EC, as well as m/z 112 --> 63 for the LEC internal standard. The limits of detection and quantification were 0.6 and 1.2 microg kg(-1), respectively, and the recovery of the method was 101 +/- 10% at 10 microg kg(-1) and 98 +/- 5% at 100 microg kg(-1). The precision of the method, established under conditions of intermediate reproducibility, did not exceed a relative standard deviation of 7%. The quantitative performance of the new GC/PICI-SRM procedure compared favourably with that of a reference method based on GC/MS and selected ion monitoring (correlation coefficient, r = 0.997). However, the new method had the advantages of reduced sample preparation time, improved sensitivity and unambiguous identification of EC at all concentrations. Application of the new method to the analysis of 50 UK breads showed that levels of EC ranged from 0.6 to 2.3 microg kg(-1) in retail products and from 3.1 to 12.2 microg kg(-1) for breads prepared using domestic breadmaking machines (dry weight basis). Toasting bread in a domestic toaster led to increases of between two- and three-fold in mean EC concentrations.     

Oxidation induced decomposition of ethylene carbonate from DFT calculations - importance of explicitly treating surrounding solvent

The oxidation induced reactions of the common lithium battery electrolyte solvent ethylene carbonate (EC) have been investigated for EC(2) using density functional theory and for selected reaction paths using M?ller-Plesset perturbation theory (MP4). The importance of explicitly treating at least one solvent molecule interacting with EC during oxidation (removal of an electron) on the EC oxidation potential and decomposition reactions was shown by comparing oxidation of EC and EC(2). Accuracy of DFT results was evaluated by comparing with MP4 and G4 values for oxidation of EC. The polarized continuum model (PCM) was used to implicitly include the rest of the surrounding solvent. The oxidation potentials of EC(2) and EC(4) were found to be significantly lower than the intrinsic oxidation potential of an isolated EC and also lower than the oxidation potential of EC-BF(4)(-). The exothermic proton abstraction from the ethylene group of EC by the carbonyl group of another EC was responsible for the decreased oxidative stability of EC(2) and EC(4) compared to EC. The most exothermic path with the smallest barrier for EC(2) oxidation yielded CO(2) and an ethanol radical cation. The reaction paths with the higher barrier yielded oligo(ethylene carbonate) suggesting a pathway for the experimentally observed poly(ethylene carbonate) formation of EC-based electrolytes at cathode surfaces.