【摘要】：貴金屬納米簇由于量子尺寸效應(yīng)表現(xiàn)出特異的光、電及化學(xué)性能從而成為納米材料熱門研究領(lǐng)域之一。由于納米簇的小尺寸、無毒性以及光穩(wěn)定性等,使其新型熒光探針在化學(xué)檢測及生物標(biāo)記等領(lǐng)域作出了突出貢獻。光催化對環(huán)境中有機物的降解/轉(zhuǎn)化過程起著重要的作用,紫外光既能進行催化還原反應(yīng),又能進行催化氧化反應(yīng)。在有機物存在下,紫外光照射有機物和銀離子混合溶液,有機物產(chǎn)生的超氧陰離子能還原銀離子制備銀納米簇。因此,本文用光還原法制備銀納米簇并應(yīng)用于無機離子和金屬離子的檢測。在紫外光下有機物變色酸易脫色/降解,研究發(fā)現(xiàn)加入微量銅離子時能抑制其脫色/降解,據(jù)此建立了紫外光照下利用變色酸檢測微量銅離子的方法。主要研究內(nèi)容如下:(1)本文以羧甲基葡聚糖為穩(wěn)定劑和還原劑,紫外光照射[Ag(NH3)2]OH溶液合成一種新型水溶性熒光銀納米簇;并對其尺寸和形貌進行了TEM,HRTEM和熒光紫外光譜表征。基于銀納米簇與鹵素離子間的特定化學(xué)反應(yīng)能夠生成Ag X沉淀導(dǎo)致銀納米簇?zé)晒忖?從而成功構(gòu)建了一種檢測鹵素離子的熒光傳感器。在BR緩沖溶液中,Br-對I-的檢測具有較強的干擾作用;在氨水條件下,該檢測方法對I-具有很高的選擇性,能夠在I-和Br-共存溶液中識別I-,并且能檢測到的I-濃度范圍為1.0×10-10~1.0×10-7 mol/L。在BR緩沖溶液中,當(dāng)I-和Br-共存時能夠檢測兩種離子的總信號響應(yīng),因此通過分別檢測BR緩沖溶液和氨水介質(zhì)下的信號響應(yīng),實現(xiàn)混合樣品中I-和Br-的同時檢測。此外,該傳感系統(tǒng)已成功地應(yīng)用于檢測海帶樣品。(2)基于Mn2+與氨水作用生成Mn(OH)2,Mn(OH)2不穩(wěn)定易被氧化為成Mn O2(不僅難溶于水而且難溶于堿溶液)。紫外光照射[Ag(NH3)2]OH溶液合成一種新型水溶性強熒光銀納米簇,當(dāng)銀納米簇中加入適當(dāng)濃度的Mn2+可以引起熒光的減弱甚至猝滅。據(jù)此,本文建立了一種在氨水條件下以熒光銀納米簇為探針,熒光分光光度法檢測Mn2+的新方法,該方法操作簡單,可靠,靈敏度高,在最佳實驗條件下檢測Mn2+的最低濃度可達1.0×10-10 mol/L。(3)基于紫外光能夠催化脫色/降解偶氮有機染料變色酸,同時偶氮型的有機物是一種很好的螯合試劑;當(dāng)變色酸中加入Cu2+時,變色酸與Cu2+生成一種穩(wěn)定的銅離子螯合物(Cu2+-CR)能夠抑制變色酸脫色/降解,據(jù)此建立了在紫外光照下以變色酸為探針檢測微量銅離子的方法。變色酸溶液的顏色和最大特征吸收峰值隨著Cu2+濃度的變化而變化,且最大特征吸收峰處吸光度的改變值(?A)與Cu2+濃度在5.0?10?9~1.0?10?6 mol/L的范圍內(nèi)呈現(xiàn)良好的線性關(guān)系,并且成功的應(yīng)用于頭發(fā)中Cu2+含量的檢測。
[Abstract]:Noble metal nanoclusters have become one of the hot research fields because of their special optical, electrical and chemical properties due to their quantum size effects. Due to their small size, nontoxicity and photostability, the novel fluorescent probes have made outstanding contributions in the fields of chemical detection and biomarker. Photocatalysis plays an important role in the degradation / transformation of organic compounds in the environment. Ultraviolet light can not only catalyze the reduction reaction but also the catalytic oxidation reaction. In the presence of organic compounds, the superoxide anion produced by organic compounds can reduce silver ions to silver nanoclusters by UV irradiation of mixed solution of organic compounds and silver ions. Therefore, silver nanoclusters were prepared by photoreduction method and applied to the detection of inorganic ions and metal ions. The decolorization / degradation of organic compounds is easy to be decolorized / degraded under ultraviolet light. It is found that the decolorization / degradation of organic compounds can be inhibited by adding trace copper ions. A method for the detection of trace copper ions by chromotropic acid under ultraviolet light has been established. The main contents are as follows: (1) in this paper, a novel water-soluble fluorescent silver nanocluster was synthesized by UV irradiation with [Ag (NH3) 2] OH solution with carboxymethyl dextran as stabilizer and reductant, and its size and morphology were characterized by TEM,HRTEM and fluorescence UV spectroscopy. Based on the specific chemical reaction between silver nanoclusters and halogen ions, a fluorescence sensor for the detection of halogen ions was successfully constructed, which resulted in the fluorescence quenching of silver nanoclusters due to the formation of Ag X precipitation. In BR buffer solution, Br- has strong interference on I- detection, and in ammonia solution, this method has high selectivity to I-, it can recognize I-in I- and Br- coexisting solution, and the concentration of I- can be detected in the range of 1.0 脳 10-10 ~ (-) 1.0 脳 10 ~ (-7) mol/L.. In BR buffer solution, the total signal response of the two ions can be detected when I- and Br- coexist, so the detection of I- and Br- in mixed samples can be realized by detecting the signal responses in BR buffer solution and ammonia solution respectively. In addition, the sensing system has been successfully applied to the detection of kelp samples. (2) based on the interaction of Mn2 and ammonia, Mn (OH) _ 2 mn (OH) _ 2 instability is easily oxidized to Mn O _ 2 (not only insoluble in water but also insoluble in alkali solution). A new type of water-soluble strongly fluorescent silver nanoclusters was synthesized by ultraviolet irradiation of [Ag (NH3) 2] OH solution. When the appropriate concentration of Mn2 was added to the silver nanoclusters, the fluorescence intensity could be weakened or even quenched. Therefore, a new method for the detection of Mn2 using fluorescent silver nanoclusters as probe in ammonia solution has been developed. The method is simple, reliable and sensitive. Under the optimum experimental conditions, the lowest concentration of Mn2 can reach 1.0 脳 10 ~ (-10) mol/L. (3) based on ultraviolet light, it can catalyze decolorization / degradation of chromotropic acid of azo organic dyes, and azo type organic matter is a good chelating reagent. When Cu2 is added to chromotropic acid, A stable copper ion chelate (Cu2-CR) from chromotropic acid and Cu2 can inhibit decolorization / degradation of chromotropic acid. A method for the detection of trace copper ion with chromotropic acid as probe under ultraviolet light was developed. The color and maximum characteristic absorption peak of chromotropic acid solution changed with the change of Cu2 concentration, and there was a good linear relationship between the change value of absorbance at the maximum characteristic absorption peak and the concentration of Cu2 in the range of 5.0 ~ 10 ~ 10 ~ (9) ~ 1.0 ~ (10) ~ 10 ~ (6) mol/L. And successfully applied to the detection of Cu2 content in hair.
【學(xué)位授予單位】：湖南科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O657.3;TB383.1

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相關(guān)期刊論文 前1條

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本文編號：2287385