| With the rapid development of modern industry,various problems caused by environmental pollution have been brought about in our world past two decades. Transportation of environmental pollutants led to the serious pollution to the air, water,soil and everywhere.Consequently,environment prevention has become a global issue.Aromatic amines are important environmental pollutants which were classified as preferential supervised environmental pollutants.Mutagencity and carcinogenicity of aromatic amines to human body has put a serious threaten to our health.Aromatic amines are widely used in industry to produce medicine,agricultural chemicals,fine chemicals,typically various synthetic dyestuffs etc.Such pollutants were discharged into the environmental atmosphere via many ways which resulted in a global decline in the quality of the environment.Aromatic amines are mainly released out with waste water and rubbish.Particularly,printing and dyeing industrial waste water containing high concentrations of aromatic amines intermediates,and some dyes were also degraded and finally released aromatic amines through chemical reactions and the effect of micro-organisms,which resulted in a wide range of environmental pollution.In addition to industrial pollution,people often contact with the textile dyes and cosmetics in daily life with dangerous crisis behind the colorful make-up.Moreover,some aromatic amines could also lead to food safety issues from certain contaminated packaging materials.People have difficulty in finding aromatic amines harmfulness when they are enjoying colorful life.Therefore,to establish, develop and perfect the effective analytical methods of the above pollutants become an imperative task and hot overlapping research area in analytical chemistry and environmental chemistry.The research results are expected to provide a useful tool for the environmental science.In this thesis,the new methods of determinating aromatic amines pollutant were developed by high performance liquid chromatography-mass spectrometric method (HPLC-ESI-MS).The established methods have high sensitivity,high selectivity and rapid qualitative and quantitative analysis.It can improve the reliability of the analysis method and facilitate to the determination of trace aromatic amines pollutants in waste water and dyeing textile products.The methods were also applied to monitor aromatic amines in simulated sweat,alkaline detergent soak solution of dyeing textile products in order to study the migration behavior of aromatic amines under a common condition.Meanwhile,the interaction between BSA and aromatic amines were studied by fluorescence spectroscopic method so as to understand the toxicological aspects of aromatic amines to life body.The main content is as follows:1 First of all,physical and chemical properties and harmfulness to human being of aromatic amines were introduced,and then focused on the recent progress review of their analytical methods,and the necessity of developing new methods was elaborated.The structures,functions and property of proteins were introduced briefly.Meanwhile,the research methods and contents of interaction between serum albumins and common chemicals or drugs were summarized.All works contribute as current research base.2 Without water,without life.Water is precious natural resource for our sustainable development and offspring.Current strict discharge standards(GB8978-1996) were issued in China.However,the related validation analytical methods for monitoring aromatic amines pollutants were required to be perfect in the future. Hereafter,a new method for the determination of five aromatic amines including benzdine,aniline,p-toluidine,p-nitroaniline,andα-naphylamine in wastewater was developed by high performance liquid chromatography coupling with mass spectrometry(HPLC-ESI-MS).The chromatographic separation was carried on a Kromasil C18 column using methanol-5mmol/L ammonium formate buffers (pH=3.0) as mobile phases at a flow rate of 1mL/min in a gradient elution mode and split sampling.The mass spectrometric quantitative analysis based on selective ionic measurement[M+H]+ by electro-spray ionization in positive mode. The calibration curves for five aromatic amines were rather linear over a range of 7.03～281.30μg/L,10.65～213.10μg/L,11.91～238.20μg/L,12.39～247.90μg/L and 14.55～291.10μg/L,respectively.The average recoveries were 92.7%～101.4%by standard spiking.The detection limits(S/N=2) varied from 1.7μg/L to 3.2μg/L. The results show that the method has high sensitivity,simple pretreatment and wide linear range.It can be used as a rapid and sensitive analysis for the above aromatic amines in wastewater samples.3 Azo dyes are the most important category of dyes,people frequently contact with it through clothing in daily life,it can easily be transfered into aromatic amines in human body,and harm human health.A new method for the determination of aromatic amines,including benzidine,4,4'-diaminobiphenymethane, 3,3'-dimethoxybenzidine,3,3'-dimethylbenzidine,4,4'-thiodianiline,in dyed textiles samples was developed by LC-MS.The chromatographic separation was carried on a Kromasil C18 column by using methanol-5mmol/L ammonium formate buffer(pH=6.0) as mobile phase at a flow rate of 1ml/min in gradient elution mode and split sampling.The mass spectrometric quantitative analysis based on selective ionic measurement[M+H]+ by electro-spray ionization in positive mode.The calibration curves for benzidine,4,4'-diaminobiphenymeth ane,3,3'-dimethoxybenzidine and 3,3'-dimethylbenzidine were linear within the range of 5～200μg/L,while 10～200μg/L for 4,4'-thiodianiline.Their average recoveries from the extraction of azo-dyed textiles were 92.7%～101.4%by standard spiking.The detection limitations were from 1.7μg/ to 3.2μg/.The results showed that the proposed method is sensitive,simple for pretreatment and wide for linear range.It should be suitable as a fast and sensitive analysis for the above aromatic amines in dyed textile samples.4 Some simulation experiment on the migration behavior of five aromatic amines in azo-dyed textiles was also carried out by determination their concentrations in the immersed simulating sweat solution and laundry soap powder from time to time based on LC-MS method so that warn and prevent the pollutants.New quantitive method dealt with SIR mode and sectionalized acquisition with high selectivity and sensitivity.The calibration curves for p-Chloroaniline,4,4'-Diaminobipheny-methane, o-Toluidine,4,4'-Oxydianiline,and benzidine were linear within the range of 12.75～2552.00μgL-1,13.71～2741.00μgL-1,22.18～2218.00μgL-1, 27.34～2734.00μgL-1 and 24.72～2472.00μgL-1,respectively.The average recoveries were 71.3%～92.2%by standard spiking.The results showed that aromatic amines in dyed textile samples can easily migrate into simulation sweat and laundry soap powder.5 The interaction between bovine serum albumin(BSA) and aromatic amines was studied by fluorescence spectrometric and mass spectrometric methods.The results indicated that BSA can combine with aromatic amines,such as p-nitroaniline,benzidine and 4,4'-diaminobiphenymethane.The SIR[M+H]+ peak of p-nitroaniline became weaker and weaker while combining with BSA was also observed.Meanwhile,a quenching fluorescenitc spectrum of BSA was accompanied following common static quenching mechanism.Some binding constants and thermodynamic parameters of BSA with p-nitroaniline were obtained at different temperatures.The distance of their binding sites were determined by the calculation according to the theory of F(o|¨)rster's non-radiative energy transfer.Based on the results analysis,it could be concluded that the hydrophobic interaction between BSA and p-nitroaniline was the main combination forces.Additionally,the effect of p-nitroaniline on the conformation of BSA was also investigated by synchronous fluorescence spectrometry.It can be deduced that the p-nitroaniline might penetrate into the hydrophobic zone of BSA and lead to slight conformation change,which should be responsible for the biochemical toxicity of aromatic amines.
|
PDF Full Text Request