發(fā)布時間：2018-05-31 14:42

  本文選題：共振瑞利散射 + 熒光光譜法��； 參考：《重慶三峽學(xué)院》2017年碩士論文

【摘要】：農(nóng)藥是用于防治危害農(nóng)作物及農(nóng)副產(chǎn)品的病蟲害、野雜草及其它有害生物的化學(xué)藥品的統(tǒng)稱,它們可來源于人工合成的化合物,也可來源于自然界的天然產(chǎn)物。農(nóng)藥作為一種兩面性物質(zhì),其對農(nóng)業(yè)生產(chǎn)或衛(wèi)生除害方面有益,但同時也會造成環(huán)境污染問題,迫害生態(tài)環(huán)境健康或人體健康。世界各國都出臺了相關(guān)的標(biāo)準(zhǔn),規(guī)定了各種農(nóng)藥在各環(huán)境中的最大殘留量,或是規(guī)定了每日允許攝入量。這充分說明了人們對農(nóng)藥污染問題非常的重視,對農(nóng)藥對人體健康的影響十分的關(guān)注。因此,分析測定各環(huán)境中農(nóng)藥殘留對于保護生態(tài)環(huán)境健康或人體健康來說是至關(guān)重要和必要的。本研究主要是借助分子光譜手段(共振瑞利散射技術(shù)和熒光光譜法)分析與測定環(huán)境中的農(nóng)藥殘留。目前市場上所售賣的手性農(nóng)藥約占農(nóng)藥種類的40%。而本實驗主要的研究對象就是手性農(nóng)藥馬拉硫磷、精喹禾靈,以及農(nóng)藥草甘膦。研究了分析對象與光探針試劑(色氨酸、曙紅Y、氯化鈀以及硝酸銅)之間相互作用對體系共振瑞利散射或體系熒光的影響。本文考察了光譜特征、最佳的反應(yīng)條件及其相關(guān)的影響因素,分別建立了共振瑞利散射技術(shù)對手性農(nóng)藥馬拉硫磷或精喹禾靈進行測定,建立了熒光光譜法對農(nóng)藥精喹禾靈或草甘膦進行測定,并且對體系的反應(yīng)機理、散射增強以及熒光猝滅等原因分別進行了研究和討論。并且將建立的方法運用到實際樣品的測定中,結(jié)果較為滿意。本文在國家自然科學(xué)基金(No.21175015;No.21475014)的資助下完成,其主要研究內(nèi)容如下:1.色氨酸-Pd(Ⅱ)-馬拉硫磷三元體系的熒光和共振瑞利散射光譜研究及其分析應(yīng)用基于色氨酸-氯化鈀-馬拉硫磷體系的共振瑞利散射(RRS)增強建立了一種方便、簡單快速的方法用以測定農(nóng)藥馬拉硫磷。利用熒光光譜、共振瑞利散射技術(shù)以及紫外-可見吸收光譜研究了色氨酸、氯化鈀(Pd(Ⅱ))和馬拉硫磷三者之間的反應(yīng)。在最佳的反應(yīng)條件下,色氨酸-鈀-馬拉硫磷體系的共振瑞利散射顯著增強,這是由于馬拉硫磷的酸解產(chǎn)物與鈀和色氨酸通過靜電作用和疏水作用結(jié)合生成了新的三元螯合物,從而導(dǎo)致體系的共振瑞利散射增強,且增強的強度與馬拉硫磷的濃度在一定的范圍內(nèi)呈線性關(guān)系。同時還考察了共存物質(zhì)對體系共振瑞利散射的影響,結(jié)果表明體系具有良好的抗干擾能力。新創(chuàng)建的共振瑞利散射方法可以用于實際樣品中馬拉硫磷的測定,且結(jié)果較為滿意。2.氯化鈀-精喹禾靈二元體系的共振瑞利散射、二級散射和倍頻散射光譜研究及其分析應(yīng)用利用共振瑞利散射技術(shù)、二級散射技術(shù)、倍頻散射技術(shù)以及紫外-可見吸收光譜研究了氯化鈀(Pd(Ⅱ))和精喹禾靈(Qpe)間的相互反應(yīng)�；诠庾V圖的變化,我們可以推斷在最佳反應(yīng)條件下,氯化鈀和精喹禾靈間反應(yīng)生成了 Pd(Ⅱ)-Qpe離子締合物,從而導(dǎo)致體系的共振瑞利散射、二級散射、倍頻散射顯著增強。散射增強的強度與精喹禾靈的濃度在一定范圍內(nèi)呈正比例關(guān)系。實驗還考察了共存物質(zhì)對體系共振瑞利散射的影響,結(jié)果表明體系具有良好的抗干擾能力。因此,建立了測定精喹禾靈的共振瑞利散射方法、二級散射法和倍頻散射法。共振瑞利散射法測定精喹禾靈的檢出范圍為0.2-1.4μg/mL,最低檢出限為55.4 ng/mL。實驗討論了氯化鈀和精喹禾靈間可能的反應(yīng)機理和共振瑞利散射增強的原因。共振瑞利散射法較其它方法有較好的選擇性,可以成功的用于實際樣品中精喹禾靈的測定,且結(jié)果令人滿意。3.曙紅Y作光探針的熒光猝滅法測定精喹禾靈的研究及其分析應(yīng)用一種方便、簡單快速的測定精喹禾靈的熒光猝滅法得以建立。曙紅Y(EY)是一種紅色染料,具有較強的綠色熒光(λex/λem = 519/540 nm)。利用熒光光譜、共振瑞利散射技術(shù)以及紫外-可見吸收光譜研究了曙紅Y、氯化鈀(Pd(Ⅱ))和精喹禾靈三者之間的相互反應(yīng)。根據(jù)光譜圖的變化,可以推斷Pd(Ⅱ)與Qpe反應(yīng)提供了帶正電荷的螯合物,然后通過靜電作用和氫鍵作用與帶負(fù)電荷的EY反應(yīng)生成三元螯合物。在最佳條件下,有Pd(Ⅱ)存在的曙紅Y體系熒光可以被精喹禾靈猝滅且體系RRS信號顯著增強,熒光強度和RRS強度變化與精喹禾靈的濃度呈一定線性關(guān)系�；隗w系的熒光猝滅,建立了一種新穎、方便的熒光法用于測定精喹禾靈。該法測定精喹禾靈的檢出范圍為0.04-1.0 μg/mL,最低檢出限為20.3 ng/mL。把該法與其它方法比較,具有較高的靈敏度和較大的檢出范圍。同時實驗也考察了共存物質(zhì)對體系的影響,結(jié)果表明體系具有良好的抗干擾能力。新創(chuàng)建的共振瑞利散射方法可以用于實際樣品中精喹禾靈的測定,且結(jié)果較為滿意。4.色氨酸作光探針的熒光"關(guān)-開"法測定草甘膦的研究及其分析應(yīng)用色氨酸(Try)作為一種芳香烴氨基酸,具有較強的熒光(λex/λem = 279/355 nm)。色氨酸熒光在pH為6.24的磷酸鹽(Na2HP04-KH2PO4)緩沖溶液中可被鈀離子(Pd(Ⅱ))顯著猝滅,在pH為8.67的磷酸鹽緩沖液中可被銅離子(Cu(Ⅱ))顯著猝滅,同時向兩體系中加入農(nóng)藥草甘膦(Gly),體系的熒光都得到恢復(fù)。對比在最佳條件下Try-Pd(Ⅱ)體系和Try-Cu(Ⅱ)體系測定草甘膦,Try-Cu(Ⅱ)體系具有較好的靈敏度、準(zhǔn)確性以及抗干擾能力。實驗分別討論了 Try-Pd(Ⅱ)體系和Try-Cu(Ⅱ)體系中各物質(zhì)間的反應(yīng),考察了各體系最佳的反應(yīng)條件,同時也詳細(xì)的研究了共存物質(zhì)對體系的影響。Try-Cu(Ⅱ)體系測定草甘膦的檢出范圍為0.025-1.0 μg/mL,最低檢出限為8.6 ng/mL。把創(chuàng)建的方法用于實際樣品中草甘膦的測定,結(jié)果表明,Try-Cu(Ⅱ)體系對草甘膦的測定結(jié)果更有效、更準(zhǔn)確。因此,基于色氨酸熒光的"關(guān)-開"效應(yīng),建立了簡單、快速測定草甘膦的熒光光譜法。
[Abstract]:Pesticides are used to prevent and control diseases and pests of crops and agricultural and sideline products, the chemical drugs of wild weeds and other harmful organisms. They can be derived from synthetic compounds and natural natural products. As a two sided substance, pesticides are beneficial to agricultural production or sanitation, but they will also be used. Environmental pollution problems, persecuting the health of the ecological environment or human health, all countries in the world have issued relevant standards, which stipulate the maximum amount of pesticide residues in the environment, or the daily allowable intake. This fully illustrates that people pay great attention to the problem of pesticide pollution and the effect of pesticide on human health. Therefore, the analysis and determination of pesticide residues in various environments is essential and necessary for the protection of ecological environment health or human health. This study is mainly based on molecular spectroscopy (resonance Rayleigh scattering and fluorescence spectrometry) for the analysis and determination of pesticide residues in the environment. The main object of this study is 40%., the chiral pesticide malathion, praziprine, and pesticide glyphosate. The effects of the interaction between the analysis object and the light probe reagents (tryptophan, eosin Y, palladium chloride and copper nitrate) on the system resonance Rayleigh scattering or system fluorescence are studied. Characteristics, the optimum reaction conditions and the related factors, the resonance Rayleigh scattering technique was established to determine the adversary pesticide malathion or quetialine respectively. The fluorescence spectrometry was established for the determination of quetialine or glyphosate, and the reaction mechanism, the scattering enhancement and the fluorescence quenching were respectively introduced. The research and discussion are carried out and the method is applied to the determination of actual samples. The results are satisfactory. The main contents of this paper are as follows: the fluorescence and Resonance Rayleigh scattering spectra of 1. tryptophan -Pd (II) -Pd (II) - malathion system and the study of the resonance Rayleigh Scattering Spectra. Based on the resonance Rayleigh scattering (RRS) enhancement of tryptophan palladium chloride malathion system, a convenient, simple and fast method was established for the determination of malathion in the pesticide. The fluorescence spectra, resonance Rayleigh scattering and UV visible absorption spectra were used to study the three cases of tryptophan, palladium chloride (Pd (II)) and malathion. In the optimum reaction conditions, the resonance Rayleigh scattering of the tryptophan palladium malathion system is enhanced significantly, due to the formation of a new three element chelate by the combination of palladium and tryptophan by the combination of palladium and tryptophan by electrostatic interaction and hydrophobicity, resulting in enhanced resonance Rayleigh scattering of the system and the intensities and intensities of the system. The concentration of malathion is linear in a certain range. The effect of the coexistent substance on the resonance Rayleigh scattering of the system is also investigated. The results show that the system has good anti-interference ability. The newly created Resonance Rayleigh scattering method can be used for the determination of malathion in the actual samples, and the results are more satisfactory for.2. palladium chloride arginine. The resonance Rayleigh scattering of the two element system, the study of the two stage scattering and frequency doubling scattering spectrum and its application, the interaction between palladium chloride (Pd (II)) and quetialine (Qpe) is studied by Resonance Rayleigh scattering, two order scattering, frequency doubling scattering and UV visible absorption spectroscopy. It is inferred that the inter reaction of palladium chloride and ququinaline produced the Pd (II) -Qpe ionic association under the optimal reaction conditions, which resulted in the resonance Rayleigh scattering of the system, the two stage scattering, and the significant enhancement of the frequency doubling scattering. The intensity of the scattering enhancement was proportional to the concentration of quaziprine in a certain range. The experiment also examined the coexisting substance pair. The effect of Resonance Rayleigh scattering shows that the system has good anti-interference ability. Therefore, the resonance Rayleigh scattering method for the determination of quetialine, two stage scattering and frequency doubling scattering, the detection range of quetialine by Resonance Rayleigh scattering method is 0.2-1.4 mu g/mL, and the minimum detection limit is 55.4 ng/mL., and the chlorination is discussed. The possible mechanism of the reaction between palladium and quetialine and the reason for the enhancement of Resonance Rayleigh scattering. The resonance Rayleigh scattering method has better selectivity than the other methods. It can be successfully used for the determination of ququprazine in actual samples, and the results are satisfactory and the fluorescence quenching method of.3. eosin Y as a light probe for the determination of quetialine and its analysis should be satisfactory. A convenient, simple and fast fluorescence quenching method for the determination of quaziprine was established. Eosin Y (EY) was a red dye with a strong green fluorescence (lambda ex/ EM = 519/540 nm). The three cases of eosin Y, palladium chloride (Pd (II)) and quetialine were studied by fluorescence spectroscopy, resonance Rayleigh scattering and UV visible absorption spectra. The interaction between the Pd (II) and the Qpe reaction provides a positive charge chelate, and then the three element chelate is generated by the electrostatic interaction and hydrogen bonding with the negatively charged EY reaction. Under the optimum conditions, the eosine Y system fluorescence in Pd (II) can be quenched by the fine quinolin and the system RRS signal The fluorescence intensity and the intensity of RRS were linearly related to the concentration of ququinoline. Based on the fluorescence quenching of the system, a novel and convenient fluorescence method was established for the determination of ququprazine. The detection range of ququprazine was 0.04-1.0 g/mL, and the minimum detection limit was 20.3 ng/mL.. The method was compared with other methods. The results show that the system has good anti-interference ability. The newly created Resonance Rayleigh scattering method can be used for the determination of kququazine in actual samples, and the results are more satisfied with the fluorescence of.4. tryptophan as a light probe. The study and analysis of glyphosate by method and its analysis and application of tryptophan (Try) as an aromatic amino acid with strong fluorescence (lambda ex/ lambda EM = 279/355 nm). The fluorescence of tryptophan in a phosphate (Na2HP04-KH2PO4) buffer solution of pH 6.24 can be significantly quenched by palladium ions (Pd (II)) and can be copper ions in the phosphate buffer solution of pH 8.67. Cu (II)) was significantly quenched. At the same time, the fluorescence of the system was restored by adding pesticide glyphosate (Gly) into the two system. Compared with the optimum conditions, the Try-Pd (II) system and the Try-Cu (II) system were used to determine glyphosate, and the Try-Cu (II) system had good sensitivity, accuracy and anti-interference ability. The experiment discussed the Try-Pd (II) system and Try-Cu (Try-Cu (II) respectively. II) the reaction between the various substances in the system, the optimum reaction conditions of each system were investigated, and the effects of the coexisting substances on the system were also studied in detail. The detection range of glyphosate was 0.025-1.0 g/mL, and the minimum detection limit was 8.6 ng/mL.. The established method was used for the determination of glyphosate in actual samples. The results showed that the method was used for the determination of glyphosate in the actual samples. The Try-Cu (II) system is more effective and more accurate for the determination of glyphosate. Therefore, based on the "turn off" effect of tryptophan fluorescence, a simple and fast fluorescence spectrometric method for the rapid determination of glyphosate is established.
【學(xué)位授予單位】：重慶三峽學(xué)院
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.3;X839.2

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