增感效应导数火焰原子吸收光谱测定金属铜和铜合金中的微量铬

提出了增感效应导数火焰原子吸收光谱测定金属铜和铜合金中微量铬的新方法。研究了表面活性剂十二烷基硫酸钠对铬的增感效果。导数技术与增感效应相结合的可使火焰原子吸收光谱的灵敏度提高６８倍。本法测定金属铜和铜合金中的微量铬取得了满意效果。     

表面活性剂在火焰原子吸收光谱法中增感效应的研究

表面活性剂在火焰原子吸收光谱法中的应用及理论研究目前非常活跃,但表面活性剂对元素产生增感效应的原因尚未弄清,本文研究了不同类型表面活性剂对元素吸光度值的影响,发现除碱金属元素外,表面活性剂对金属元素是否产生增感效应与元素在火焰中的原子化效率有关,进而对其增感机理做了探讨。     

火焰原子吸收分析中表面活性剂对锰吸收讯号的增感效应及机理

提出了一种新的增感机理:在表面活性剂的cmc前,气溶腔形成过程中被测离子在小液滴上富集产生增惑;cmc后富集作用减小,但被测离子和表面活性剂形成胶团化物产生新的增感,火焰部分表面活性剂的不完全燃烧增强了火焰的还原性是增感因素之一。     

气相色谱法测定聚氧乙烯型非离子表面活性剂中环氧乙烷的加成数

聚氧乙烯型非离子表面活性剂中环氧乙烷的加成数多少,直接决定或影响该活性剂的性能。它的测定是引人注目的分析工作。目前理想的分析方法报导较少。常采用薄层色谱法测定,但该法误差大,操作条件难以控制,且需标准物;而RPLC法及MS法尚难以用于生产实践。     

火焰原子吸收光谱法测定红花中的Cu、Fe、Zn

采用火焰原子吸收光谱法和表面增敏的方法测定了红花中Cu、Fe、Zn的含量。实验表明,使用表面活性剂十二烷基硫酸钠(SDS),可使Zn的吸光度增感34.91%,使Cu增感37.39%,Fe增感232.10%。该法的检测限分别为Zn1.85×10-3μg/mL;Fe1.50×10-2μg/mL;Cu3.50×10-2μg/mL,加标回收率在99.37%~104.23%之间。该法灵敏度高,结果准确,可用于红花等中草药中Cu、Fe、Zn的同时测定。     

增感效应火焰原子吸收光谱法测定 铁矿石中的微量铬

提出了增感效应火焰原子吸收光谱测定铁矿石中微量铬的新方法。研究了表面活性剂十二烷基硫酸钠(SDS)对铬的增感效果。增感效应可使火焰原子吸收光谱的灵敏度提高 27倍。本法已用于测定铁矿石中的微量铬,检测限为 7.0μg/L ,回收率为 91.1%～115.9%,RSD为 4.0%。     

增感效应火焰原子吸收光谱法测定铁矿石中的微量铬

提出了增感效应火焰原子吸收光谱测定铁矿石微量铬的新方法。研究了表面活性剂十二烷基硫酸钠（ＳＤＳ）对铬的增感效果。增感效应可使火焰原子吸收光谱的灵敏度提高２７倍。本法已用于测定铁矿石中的微量铬,检测限为７．０μｇ／Ｌ,回收率为９１．１％￣１１５．９％,ＲＳＤ为４．０％。     

薄层色谱法测定聚氧乙烯型阴离子表面活性剂氧乙烯数分布

含有聚氧乙烯链(EO)的阴离子表面活性剂(a-S_a)兼有阴离子和非离子两类活性剂共同的优点,近年来在石油、轻工和化工行业中获得了广泛的应用。环氧乙烷的阶梯式加成,使这类a-S_a的加成产品成为具有一定EO数分布而非单一聚合度的调聚物。因EO加成数的多少及EO数的分布情况对活性剂的物化性能有很大影响,因此需要测定其EO数分布及纯度。 对聚氧乙烯型非离子表面活性剂EO数分布的测定,国内外已做了许多工作,而对a-sa EO数分布的测定目前很少报道。本文采用薄层色谱法(TLC)的一维展开和二维展开而不经断链反应测定     

表面活性剂增敏荧光光度法测定牛奶中的三聚氰胺

建立了表面活性剂增敏荧光光度法测定牛奶中三聚氰胺的方法。利用弱碱性介质中阳离子表面活性剂(CTMAB)对三聚氰胺荧光强度的增敏作用,在pH=8.0的Tris-HCl缓冲溶液中,以CTMAB为增敏剂,测定三聚氰胺,线性范围为25～1000μg/L,检出限为19μg/L,相对标准偏差为1.6%。按国标方法处理样品,采用本法测定,回收率偏高;利用自制固相萃取整体柱对牛奶样品进行预处理后,实际样品检测获得满意结果。此方法简便、快捷、准确,可用于大量牛奶样品中三聚氰胺的快速初筛及检测。     

阴离子和非离子表面活性剂增感效应原子吸收光谱法测定铬

空气-乙炔火焰原子吸收光谱法测定铬,易受灵敏度低、基体干扰的限制。70年代中期有人提出应用表面活性剂之后,使这一测定得到了改善。本实验选用阴离子表面活性剂十二烷基硫酸钠(SLS)和非离子表面活性剂乙二醇辛基苯基酚(OP-10)、曲拉通X-100(Triton X-100)对铬的空气-乙炔火焰原子吸收光谱法的增感     

Thermodynamic and Spectroscopic Study of the Adduct Formation of Tris(β-diketonato)lanthanoids with Heteroamines

A remarkable enhancement of the extraction of lanthanoids(Ⅲ)(Ln) with β-diketones in the presence of a Lewis base, so-called synergistic effects, would be caused by the adduct formation of the β-diketonates with the Lewis base. The trend of the variation of the adduct formation constants across the lanthanoid series may be different among β-diketones used. It has also been observed that the trend across lanthanoid series and also the values of the enthalpy change in the adduct formation of the 2-thenoyltrifluoroacetonates(TTA) with 1,10-phenanthroline(phen) are very similar to those with 2,25-bipyridyl(bpy), although the values of the adduct formation constants with the former are larger than those with the latter.     

Enhanced fluorescence of triphenylmethane dyes in aqueous surfactant solutions at supramicellar concentrations--effect of added electrolyte

The colour change of triphenylmethane (TPM) dyes induced by surfactants at concentrations much greater than their critical micellar concentrations is found to be accompanied by enhanced fluorescence. Thus, the otherwise weak fluorescence of TPM dyes can be detected using supramicellar surfactant concentrations. In this respect, the nonionic polyoxyethylene (POE) chain-containing surfactants are found to be more efficient compared with ionic surfactants. The POE surfactants, Triton X-100, Tween-20 and Tween-60 present a polymer-like surface to the dyes, which can thus easily bind to them. At supramicellar concentrations, the hydrophobic environment formed in these micelles is effective in preventing nonradiative relaxation processes of the dyes. As a result, there is enhanced fluorescence for even micromolar concentrations of the dyes. Among the Tween series, Tween-60 being more hydrophobic leads to greater fluorescence enhancement than Tween-20. From the fluorescence properties, binding constants for dye binding to the surfactants can be determined. Thus the relative efficiency of these surfactants as binding substrates can be assessed. Another interesting observation is that the electrolyte LiCl in presence of the surfactants leads to even larger fluorescence enhancement than the surfactants alone.     

Enhancement of DNA compaction by negatively charged nanoparticles: effect of nanoparticle size and surfactant chain length

We study the compaction of genomic DNA by a series of alkyltrimethylammonium bromide surfactants having different hydrocarbon chain lengths n: dodecyl-(DTAB, n=12), tetradecyl-(TTAB, n=14) and hexadecyl-(CTAB, n=16), in the absence and in the presence of negatively charged silica nanoparticles (NPs) with a diameter in the range 15-100 nm. We show that NPs greatly enhance the ability of all cationic surfactants to induce DNA compaction and that this enhancement increases with an increase in NP diameter. In the absence of NP, the ability of cationic surfactants to induce DNA compaction increases with an increase in n. Conversely, in the presence of NPs, the enhancement of DNA compaction increases with a decrease in n. Therefore, although CTAB is the most efficient surfactant to compact DNA, maximal enhancement by NPs is obtained for the largest NP diameter (here, 100 nm) and the smallest surfactant chain length (here, DTAB). We suggest a mechanism where the preaggregation of surfactants on NP surface mediated by electrostatic interactions promotes cooperative binding to DNA and thus enhances the ability of surfactants to compact DNA. We show that the amplitude of enhancement is correlated with the difference between the surfactant concentration corresponding to aggregation on DNA alone and that corresponding to the onset of adsorption on nanoparticles.     

Micellar enhancement of benzodiazepine fluorescence

The interactions that exist between benzodiazepines and surfactants provide micellar enhancement factors for their fluorimetric determination in the range 1.2-6.5, depending on the nature of both the benzodiazepine and the surfactant. A series of benzodiazepines and anionic surfactants were treated topologically to determine the influence of each benzodiazepine substituent on the basic benzodiazepine structure and the influence of both the hydrophobic moiety of the surfactant and its counter ion on the sensitisation process. Sensitisation parameters were used to quantify the effect of the chemical structures of both surfactants and drugs on their interaction.     

N-Alkylnicotinium halides: A class of cationic matrix additives for enhancing the sensitivity in negative ion Fast-Atom bombardment mass spectrometry of polyanionic analytes

The addition of some surfactants to the fast-atom bombardment (FAB) matrix previously has been demonstrated to enhance analyte signals in fast-atom bombardment mass spectrometry. In particular, cationic surfactants appear to enhance the negative ion FAB detectability of analytes that exist as anionic species in the matrix solution. It has been proposed that the charged surfactant concentrates the oppositely charged analyte near the surface, which results in larger signals for the analyte. Cationic surfactants that contain a fixed positive charge and an additional basic site were prepared with different hydrophobic moieties and were evaluated for their effectiveness as FAB matrix additives. The compound N-octylnico-tinium bromide (ONBr) is shown to improve greatly the analyte-related signals in negative ion fast-atom bombardment mass spectrometry for a variety of polyanionic analytes, relative to other surfactants (e.g., cetylpyridinium salts). This surfactant not only enhances detectability, but also simplifies the pseudomolecular ion region of the resulting spectra by reducing or eliminating metal cation adduct peaks. The simple mechanism of enhancement via surface activity is evaluated, and alternative mechanisms are considered. It is clearly shown that ONBr, as a FAB matrix additive, will allow mass spectrometry to be used for the analysis of anionic compounds that normally exhibit very low responses.     

Study of adduct ions of meso-phenyl-substituted tetrabenzoporphyrins by fast-atom bombardment mass spectrometry

Mass spectra of meso-phenyl-substituted tetrabenzoporphyrins were investigated by fast-atom bombardment mass spectrometry and tandem mass spectrometry. A cluster of adduct ions with mass-to-charge ratio values higher than the corresponding molecular ions of the porphyrins has been observed. The mass number differences among the series of cluster ions are constant depending on the para-phenyl substituents. Under certain conditions, dimers or trimers of molecular ions with low abundances have been detected. To trace the origin of the adduct ions, a series of experiments based on mass spectrometry have been carried out. The mass spectrum of tetrabenzoporphyrin showed no adduct ions with mass number differences of 90 even with the addition of phenylacetic acid. The mass spectrum of meso-tetraphenylte-trabenzoporphyrin ¹³C-labeled at the meso carbons showed adduct ions with mass number differences of 91. Product spectra of [2M + H]⁺ or [3M + H]⁺ of porphyrins exhibited adduct ions. All these results suggest that fragmentations of [2M + H]⁺ or [3M + H]⁺ may be one of the many possible routes to form the adduct ions, and the mass number differences among the series of these cluster ions should correspond to the benzyl group from the meso positions of meso-phenyl-substituted tetrabenzoporphyrins.     

Thermodynamics of micellization for partially fluorinated cationic gemini surfactants and related single-chain surfactants in aqueous solution

A series of partially fluorinated cationic gemini surfactants and their corresponding monomeric surfactants have been studied by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaH(mic)) were obtained from calorimetric curves. The CMCs of the gemini surfactants are much lower than those of the corresponding monomeric surfactants and decrease with an increase in the number of fluorine atoms on the hydrophobic chain. The micellization of partially fluorinated cationic gemini surfactants is much more exothermic than that of the corresponding monomeric surfactants. Because of the incompatibility of hydrocarbon spacer and partially fluorinated chain, DeltaH(mic) values of the surfactants with a C6 spacer are more negative than those of the surfactants with a C12 spacer. The variations in the architecture of the fluorocarbon chain segments may be the reason of the irregularities in the change of DeltaH(mic) for the gemini surfactants. Moreover, the contribution of the enthalpy generally increases with an increase in the number of fluorine atoms.     

EVALUATION OF A SERIES OF PERFLUOROALKYLATED SURFACTANTS DERIVED FROM TERTIARY AMINES: SURFACE PROPERTIES AND EMULSIFICATION OF FLUOROCARBONS

In view of their easy preparation, the physicochemical properties of a series of highly fluorinated cationic (ammonium salts), zwitterionic (carboxybetaines) or nonionic (amine oxide) surfactants derived from perfluoroalkylated tertiary amines were investigated. Their solubility in water, interfacial properties and the exceptionally low hemolytic activity of the zwitterionic series mark them out as potential surfactants or co-surfactants for the preparation of fluorocarbon emulsions and other preparations for biomedical use. Fine and moderately concentrated fluorocarbon emulsions (50 w/w% in fluorocarbon) could be obtained in some cases when they were used as the sole surfactant. However, none was found suitable for preparing concentrated emulsions (90 w/v% in fluorocarbon) and no appreciable stabilization was found when they were used as co-surfactants with egg yolk phospholipids.     

Cationic surfactants for micellar electrokinetic chromatography: 1. Characterization of selectivity using the linear solvation energy relationships model

MEKC and the linear solvation energy relationship (LSER) model have been applied to two series of cationic surfactants. The synthetic flexibility of the quaternary ammonium group is exploited to generate the two series, one consisting of linear substitutions and the other incorporating the ammonium into ring structures of varying size. The effects of the head group structure on the CMC, aggregation number, and electrophoretic properties of the surfactants were determined. These surfactants were also characterized with the LSER model, which allowed the contributions of five chemical factors to the interactions between solutes and the micelles to be evaluated. Trends were observed in the cohesivity and polarity of the linear surfactant series, with both increasing with the size of the head group. No trends in the LSER parameters were observed in the cyclic series, but the LSER results do show that the surfactants with cyclic head groups provide a significantly different solvation environment from the linear series. Additional trends were observed in the aggregation behavior and chromatographic properties of the surfactants. These included changes in the CMCs, aggregation numbers, EOF, and electrophoretic mobility of the micelles that correlate to changes in head group size.     

吸电子取代基(2-硝基)金属卟啉的轴向加合反应的研究

本文报道了用电子吸收光谱和电化学方法系统地研究卟啉环上具有吸电子取代基(—NO_2)的四苯基卟啉[H_2TP(2-NO_2)P]的Zn、Ni、Cu、Co、Mn、Fe的配合物与一系列含N有机碱的加合作用,测定了加合常数、加合分子数,总结了吸电子基团对金属卟啉的轴向效应以及中心金属离子和卟啉环氧化还原性的影响。