用于癌症病人初级临床诊断的化学计量学研究

用感应耦合等离子体原子发射光谱及石墨炉原子吸收测定了正常人及癌症病人头发与血清样品中13个元素。将所得数据送入计算机, 分别用化学计量学中PLS及Gram-Schmidt多元分析方法处理了血清与头发样本。在两种情况下均得到了病人与正常人分类极其清晰的二维判别图。头发样本的判别失误率低于血清样本。头发样品取样、存储及运输容易, 也宜于进行光谱分析, 因此可将头发用作癌症初级临床诊断中的分析样品。     

儿童头发中微量元素锌、铜、铁和锰的原子吸收光谱测定

微量元素铜、锌、铁和锰是人体重要的营养元素,在体内具有重要的生理功能及营养作用。随着微量元素与人体健康学研究的不断深化,头发作为人体微量元素的次要排泄器官之一,其含量能反映个人较长时间内元素的积累状况及体内水平而受到重视。目前,国内外采用原子吸收法以及其它方法进行分析测定均有报道。在大多数原子吸收测定中,分析者都是用成年人的头发为测试样品,而对儿童头发作为测试样品很少见报道。本文研究了用火焰原子吸收光谱法测定儿童头发中微量元素铜、锌、铁和锰。该法具有操作简单、快速、准确、经济等优点。测定灵敏度、精密度好,相对标准偏差小于±3％。     

丙型病毒性肝炎感染者头发中部分微量元素的研究

为探讨丙型肝炎病毒(HCV)感染者头发部分微量元素含量的变化,用原子吸收分光光度计分别测定了HCV感染者和正常人头发中的微量元素Zn、Fe、Se含量。结果表明,抗-HCV阳性组及HCV患者组发Zn含量低于正常对照组,经统计学检验,具有高度显著性差异(P<0.01);而丙肝患者组的Fe含量显著高于健康对照组。丙肝患者组头发Se含量低于健康对照组,具有显著性差异(P<0.01)。提示微量元素Zn、Fe、Se与病毒性肝炎存在密切关系。     

原子吸收光谱法测定原发性癫痫患者头发中微量元素

通过原子吸收光谱法测定原发性癫痫患者头发中的微量元素Ｚｎ，Ｃｕ，Ｆｅ，Ｍｎ，Ｐｂ和宏量元素Ｋ，Ｎａ，Ｃａ，Ｍｇ并与正常人头发中的微量元素比较，结果表明，：癫痫患者头发中的锰含量明显高于正常人，这一结论与有关文献的结论吻合。     

火焰原子吸收光谱法测定头发和指甲中金属元素

人体的健康与营养均与微量元素密切相关,而头发和指甲又是最易得到并在一定程度上代表人体组织的特征样品。为此,本文研究了用逆王水(硝酸和盐酸为3:1)和高压密封罐溶解样品,以火焰原子吸收光谱法测定头发和指甲中的钾、钠、钙、镁、铁、铜、锌和锰等元素,并讨论了共存元素和酸度对测定的干扰及消除。试验表明,本法简便可靠,回收率在93％～106％范围,RSD小于5％。     

人工神经网络用于消化道癌症初级诊断研究

测定了正常人及消化道癌症病人头发样品１１种元素含量,然后将人工神经网络（ＡＮＮ）用于正常人与癌症患者的分类预测,并用独立预测样本作了检验,预报识别率达１００％。讨论了网络参数的选择和发样中微量元素与癌症的关系。结果表明该方法可作为消化道癌症初级诊断的一种辅助手段。     

火焰原子吸收法连续测定儿童头发中微量元素

提出了用火焰原子吸收法连续测定儿童头发中六种微量元素的方法.儿童头发经处理后,可直接用火焰原子吸收法连续测定其中的铜、锌、铁、钙、镁、锰.方法的精密度(RSD)<11 %,标准加入回收率为95.4%～103.8%,结果满意.     

100例鼻咽癌患者与健康人头发中微量元素含量的比较

用原子吸收和火焰光谱分析法检测鼻咽癌患者100例，并以本地区100例健康人及同期我院内科住院非肿瘤患者150例为对照组，进行头发锌、铜、铁，钙，镍等的含量进行测定，结果发现鼻咽癌患者头发中钙及镍的含量比对照组明显升高，而头发中锌、铜的含量明显降低。     

再障头发、血清和骨髓组织钴、锂元素含量的变化

采用原子吸收光谱技术测定再障４３例患者头发、血清和骨髓组织的钴、锂元素含量，并与急性白血病２０例、缺铁性贫血１０例和正常人４４例作对照比较，再障头发、骨髓钴、锂和血清钴含量均低于正常人，Ｐ＜０．０５，而与急性白血病和缺铁性贫血之间，以及各种类型再障之间则无差异性．再障头发锂含量与血红蛋白、红细胞数呈负相关，Ｐ＜０．０５，说明再障确实存在着钴、锂元素代谢异常．     

浙江海宁硖石健康儿童发样元素含量调查

用火焰原子吸收光谱法测定了浙江省海宁县硖石地区５００余名儿童头发中的Ｚｎ、Ｃｕ、Ｆｅ、Ｐｂ及Ｋ、Ｎａ、Ｃａ、Ｍｇ元素含量，为儿童营养研究提供了依据。     

Effect of sample pre-treatment on the determination of steroid esters in hair of bovine calves

The effect of three sample pre-treatment steps, washing, cutting and grinding on the determination of steroid esters in hair is studied. The study is performed by using hair samples obtained after pour-on application of steroid esters to bovine calves. After sample pre-treatment the hair is treated with a mild reducing agent [tris(2-carboxyethyl)phosphine hydrochloride] to extract the steroid esters. After a solid-phase extraction clean-up step the extracts are analysed by using liquid chromatography combined with triple–quadrupole mass spectrometric detection. For the washing step the use of non-organic washing solvents like (warm) water and a solution of 0.1% sodium dodecyl phosphate and organic solutions containing different percentages of methanol are tested. By using the non-organic solvents and the organic solvents with a percentage of methanol <20% the recovery results are as good as the results obtained without washing the hair. Cutting the hair samples increases the analyte recoveries of incurred steroid esters by 20% compared to the non-cut hair. The analyte recoveries of cut hair samples are about 60–80% that of ground hair samples. The obtained surface expansion of hair samples by grinding proves to be necessary in order to achieve the highest possible analyte yields. Finally the use of pressurised liquid extraction (PLE) for the extraction of steroid esters from plain (no washing, cutting or grinding) hair is investigated. The first results show lower (up to 40%) extraction recoveries in comparison with the classical solvent extraction procedures. If the limit of detection requirement is met, PLE may be an alternative for extracting large numbers of hair samples due to the short sample treatment procedure involved.     

头发检测与疑难病诊断

综述了我国用头发诊断疑难病,包括恶性肿瘤、心脑血管疾病、尘肺的研究概况。20余年来,中国科技人员创造了4类利用头发微量元素谱诊断疾病的方法。18项研究报告表明,头发微量元素谱可将癌症病人与健康人正确区分开来,为临床癌症诊断奠定了坚实的实验基础,也为利用头发样本代替血液样本作人群癌症筛查提供了理论依据;11项研究结果表明,借助头发微量元素谱,可相当准确地判别待测样本的健康属性,可以诊断和预报疾病,可以筛选高危人群,对心脑血管病的早发现、早诊断、早治疗具有重要的潜在应用价值;9项研究结果证明,测量头发元素,建立判别方法,可以从待检样品准确诊断尘肺患者和找出尘肺高危人群,并可提早3～5年对尘肺的发生作出预报。实践表明,头发检测是疑难病筛查的一种简便、经济、实用、有效的新方法。     

用多变量统计分析方法辨识肺癌患者分类中的关键元素(英文)

用逐步判别、主成分分析和聚类方法研究了根据血清和毛发样品中元素含量对正常人和肺癌患者分类中的关键元素．用主成分分析的结果表明,在肺癌患者与正常人的分类中,血清中的Ｃａ,Ｃｒ,Ｃｕ,Ｐ和Ｚｎ是关键元素,而毛发中的Ａｌ,Ｂ,Ｃｒ,Ｐ和Ｓｒ是关键元素．对于正常人和癌症患者元素之间的欧氏距离不同     

Development, validation, and application of a liquid chromatography–tandem mass spectrometry method for the determination of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol in human hair

The tobacco-specific nitrosamine metabolite 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) is a valuable biomarker for human exposure to the carcinogenic nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) in tobacco and tobacco smoke. In this work, an efficient and sensitive method for the analysis of NNAL in human hair was developed and validated. The hair sample was extracted by NaOH solution digestion, purified by C(18) solid-phase extraction (SPE) and molecularly imprinted solid-phase extraction, further enriched by reverse-phase ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) into 1.0?% aqueous formic acid, and finally analyzed by liquid chromatography-electrospray ionization tandem mass spectrometry. Good linearity was obtained in the range of 0.24-10.0?pg/mg hair with a correlation coefficient of 0.9982, when 150?mg hair was analyzed. The limit of detection and lower limit of quantification were 0.08 and 0.24?pg/mg hair, respectively. Accuracies determined from hair samples spiked with three different levels of NNAL ranged between 87.3 and 107.7?%. Intra- and inter-day relative standard deviations varied from 4.1 to 8.5?% and from 6.9 to 11.3?%, respectively. Under the optimized conditions, an enrichment factor of 20 was obtained. Finally, the developed method was applied for the analysis of NNAL in smokers' hair. The proposed sample preparation procedure combining selectivity of two-step SPE and enrichment of DLLME significantly improves the purification and enrichment of the analyte and should be useful to analyze NNAL in hair samples for cancer risk evaluation and cancer prevention in relation to exposure to the tobacco-specific carcinogen NNK.     

极谱配合吸附波测定人发微量锰和铁

采用浓硝酸-高氯酸消化法结合锰铁-乙二胺极谱配合吸附波方法测定人发微量猛铁。对各种预处理方法进行了比较研究。测定了模拟人发、混合人发、国家一级标准物质人发样品以及某些肿瘤患者的发锰铁含量,均获得了满意结果。     

Electron spin resonance (ESR/EPR) of free radicals observed in human red hair: a new,simple empirical method of determination of pheomelanin/eumelanin ratio in hair

The definition of the concentration of pheomelanin in the skin is an issue of great interest because in the case of being influenced by UV radiation, it manifests itself as a prooxidant, causing various skin disorders including melanoma that might help to explain the relatively high incidence of skin cancer among individuals with red hair. The ESR spectra of red hair samples were investigated. It was found that at low microwave power, they are characterized by two types of spectra. Red hair ESR signals result from a superposition of two spectral shapes, a singlet spectrum as a result of the existence of eumelanin and a triplet spectrum as a result of the existence of pheomelanin. At high microwave power, only triplet spectra shape was detected, caused by saturation of the eumelanin singlet. Using different concentration ratios of black to red hair, we measured ESR spectra and plotted the ratio values in each sample against a measured ‘g‐factor’ (experimental). We found that there is a linear relationship between these two parameters. So, it is evident that using these results, the concentration ratio of pheomelanin to eumelanin in a sample of hair can be easily determined by an almost noninvasive method. This can be considered a potential advantage for many practical activities compared with other invasive methods. The concentration dependence curve of pheomelanin (µg/mg) on g_exp‐factor in an ESR spectrum of hair has been designed, which allows the determination of the amount of pheomelanin in hair of any color. Copyright © 2014 John Wiley & Sons, Ltd.     

Contribution to the sample preparation in the radionuclide X-ray fluorescence analysis of hair

Methods of sample treatment in XRF analysis of hair are studied in view of the effect on analytical results. A new method is proposed based on the incomplete ashing of hair followed by pellet preparation. Its suitability is estimated on the XRF analysis of real hair samples collected from 4 healthy adults.     

Biological monitoring of arsenic in semiconductor workers

In the manufacture of integrated circuits involving semiconductors, various hazardous materials including arsenic compounds are used. This paper present an evaluation of the biological monitoring of arsenic in the urine, blood and hair of semiconductor workers. Eighty-two blood samples were obtained from research and development workers in a semiconductor factory. Thirty-one samples of urine were obtained from the same group of worker before and after a work period (one shift). Seventy-three hair samples were similarly obtained from the workers. The concentration of arsenic in each sample was determined by arsine (AsH₃) generation flame atomic absorption spectrometry after wet ashing of the sample. The mean concentration of arsenic in hair in these semiconductor workers was significantly higher than that of controls. The mean concentration of arsenic in hair from workers with a longer employment duration was higher than from those with a shorter employment duration. The mean concentration of arsenic in hair from workers engaged in epitaxial growth processes was higher than from workers engaged in other processes. The concentrations of arsenic in hair from semiconductor workers correlated with the duration of their employment. The mean concentration of arsenic in urine before a work a period (shift) was not significantly different from that of controls. The mean concentration of arsenic in urine after a work period was in fact lower than that of controls. The mean concentration of arsenic in blood was not significantly different from that of controls. The determination of arsenic in hair is therefore considered useful for the evaluation of relatively long-term exposure to arsenic in semiconductor workers.     

Diagnosis of lung cancer based on metal contents in serum and hair using multivariate statistical methods

The classification of normal and cancer groups with four multivariate methods according to metal contents in serum and hair samples has been discussed in the present paper. Results show that the four multivariate methods, stepwise discrimination analysis, principal components analysis, hierarchical cluster analysis, and stepwise cluster analysis can distinguish the two groups correctly. The independent samples of both normal and cancer groups were tested and can be distinguished correctly by the four methods. Therefore, these methods can be used as an aid for diagnosis of lung cancer according to the metal contents in serum and hair samples.