發(fā)布時(shí)間：2018-04-10 09:24

  本文選題：金銀納米　切入點(diǎn)：比色法　出處：《南昌大學(xué)》2017年碩士論文

【摘要】：貴金屬納米材料因?yàn)榫哂歇?dú)特的金屬物理化學(xué)性質(zhì)以及優(yōu)異的光學(xué)性能而被廣泛關(guān)注并且應(yīng)用于化學(xué)催化、醫(yī)用材料、傳感材料等領(lǐng)域。尤其針對(duì)于金銀納米材料,由于其光電學(xué)性質(zhì)小尺寸效應(yīng)、良好的穩(wěn)定性以及特異的生物親和性,顯示其具有很高的潛在價(jià)值,成為了熱點(diǎn)研究領(lǐng)域。本文設(shè)計(jì)了四種不同方法的金銀納米材料用于氨基酸的特異性識(shí)別,分別建立了蛋氨酸、谷胱甘肽、組氨酸的定量分析方法,研究結(jié)果包括以下幾個(gè)方面:(1)基于蛋氨酸抑制三聚氰胺誘導(dǎo)的金納米聚集而建立的可視化蛋氨酸的檢測(cè)。在優(yōu)化實(shí)驗(yàn)條件下,采用檸檬酸鈉作為還原劑和穩(wěn)定劑合成粒徑為13.0nm左右、分散性良好的AuNPs溶膠。三聚氰胺結(jié)構(gòu)中含有三個(gè)氨基,與金屬有較強(qiáng)的配位作用,因此它們通過與金納米表面的檸檬酸根負(fù)離子進(jìn)行配位體交換作用而導(dǎo)致金納米由分散狀態(tài)變?yōu)楦叨染奂癄顟B(tài),納米金溶膠的顏色由酒紅色逐漸變?yōu)樽仙罱K變?yōu)樗{(lán)色。由于蛋氨酸與金納米通過N-Au與S-Au鍵的共同作用而結(jié)合,所以隨著蛋氨酸溶液的加入,逐漸抑制了三聚氰胺誘導(dǎo)的金納米溶膠的聚集,溶液由藍(lán)色逐漸變?yōu)榫萍t色,從而實(shí)現(xiàn)對(duì)目標(biāo)氨基酸蛋氨酸快速、簡便、靈敏的定量檢測(cè)。上述傳感機(jī)理通過透射電鏡以及納米粒徑分析儀得以驗(yàn)證。試驗(yàn)結(jié)果顯示,蛋氨酸濃度的裸眼最低檢出量為0.4μM,采用紫外光譜進(jìn)行定量分析可得到其在0.1-1.0μM范圍內(nèi)的理論檢測(cè)限(LOD)為24.5nM,本方法成功應(yīng)用到了尿樣及血清中蛋氨酸的檢測(cè),平均回收率在95%-105%之間。(2)根據(jù)抑制金納米聚集設(shè)計(jì)了一種快速、靈敏的谷胱甘肽檢測(cè)方法。2.0μM的2-巰基-1-甲基咪唑作為聚集劑能夠使金納米發(fā)生明顯的聚集,同時(shí)伴隨著顏色由紅色變?yōu)樽仙俚剿{(lán)色。Cys在pH為5.8±0.1時(shí)能使AuNPs聚集,顏色發(fā)生明顯改變,由酒紅色變?yōu)樽仙?對(duì)于Hcy而言,當(dāng)pH大于11時(shí),會(huì)引起AuNPs的聚集,但是當(dāng)pH在5-7之間時(shí),則會(huì)使AuNPs處于分散狀態(tài),對(duì)于GSH而言,當(dāng)其與AuNPs混合時(shí),在pH小于4.5時(shí)與AuNPs顆粒結(jié)合的GSH的兩個(gè)羧基間發(fā)生氫鍵作用,使AuNPs發(fā)生聚集,當(dāng)pH大于4.5時(shí),由于羧基的去質(zhì)子化作用,AuNPs則不會(huì)發(fā)生聚集。由此可知,改變?nèi)芤旱膒H可有效改善本方法的選擇性,將溶液的pH調(diào)節(jié)為5.8時(shí),Cys/AuNPs和Hcy/AuNPs會(huì)發(fā)生聚集,而GSH/AuNPs仍處于分散狀態(tài)。金納米的聚集程度隨著谷胱甘肽濃度的提高而逐漸降低,金納米由藍(lán)色逐漸變?yōu)榫萍t色,肉眼可觀察到的最低谷胱甘肽檢測(cè)量為0.1μM,利用紫外光譜進(jìn)行低濃度定量分析,谷胱甘肽濃度在0.1-1.0μM范圍內(nèi)的理論檢測(cè)限為12.0 nM。該方法成功的應(yīng)用于人體血樣和尿樣中谷胱甘肽的檢測(cè),平均回收率在95%-103%之間。(3)基于谷胱甘肽抑制半胱氨酸誘導(dǎo)金納米聚集而建立的可視化谷胱甘肽的檢測(cè)。由上一個(gè)檢測(cè)谷胱甘肽的實(shí)驗(yàn)原理可知,在pH為5.8的條件下,胱氨酸,高半胱氨酸等含巰基化合物不能使其聚集亦或有較輕微的聚集,而半胱氨酸能夠使金納米發(fā)生聚集,并且隨著半胱氨酸濃度的增加,金納米顏色由酒紅色變?yōu)樽仙�。pH的大小能夠決定AuNPs是否聚集以及聚集程度,因此選用半胱氨酸作為聚集劑,有趣的是,谷胱甘肽和半胱氨酸經(jīng)常由于結(jié)構(gòu)類似而難以區(qū)分,而在此體系中,設(shè)計(jì)的實(shí)驗(yàn)本身就能夠?qū)烧邊^(qū)分開來。當(dāng)加入谷胱甘肽后,隨著谷胱甘肽的不斷加入,溶液顏色逐漸由紫色變?yōu)榫萍t色,從而實(shí)現(xiàn)對(duì)谷胱甘肽的定量檢測(cè)分析。該方法成功地應(yīng)用于人體血樣和尿樣中谷胱甘肽的檢測(cè),平均回收率在90%-110%之間。(4)利用對(duì)氨基苯磺酸修飾的銀納米(AgNPs)對(duì)組氨酸(His)進(jìn)行了比色檢測(cè)。在優(yōu)化實(shí)驗(yàn)條件下,采用硼氫化鈉還原法合成粒徑為6.7 nm左右、分散性良好的SAA-AgNPs探針。通過透射電鏡、紅外光譜以及紫外光譜對(duì)其結(jié)構(gòu)進(jìn)行了表征,本實(shí)驗(yàn)利用組氨酸誘導(dǎo)SAA-AgNPs溶膠的聚集,從而達(dá)到定量檢測(cè)組氨酸的目的。首先,我們發(fā)現(xiàn)His有咪唑環(huán),而SAA有芳香環(huán),我們推測(cè)咪唑環(huán)和芳香環(huán)之間的π-π鍵堆積作用會(huì)使SAA-AgNPs發(fā)生一定程度的聚集,其次,SAA上的氨基與His的羧基之間的靜電作用對(duì)于SAA-AgNPs的聚集也是必不可少的,最后,對(duì)氨基苯磺酸作為識(shí)別功能團(tuán)與組氨酸通過氫鍵作用同樣對(duì)銀納米發(fā)生聚集起到了一定的作用。根據(jù)以上機(jī)理,隨著組氨酸濃度的增加,銀納米顏色由亮黃色變?yōu)殚偕俚阶仙?通過顏色變化和紫外吸收光譜變化分別實(shí)現(xiàn)了組氨酸的定性和定量分析,在0-3.5μM范圍內(nèi)其的檢測(cè)限為52.7nM,能夠成功的運(yùn)用于實(shí)際血清樣品的檢測(cè),血清樣品回收率為97%-107%之間。
[Abstract]:Noble metal nano materials because of its unique physical and chemical properties of the metal and excellent optical properties and have been widely concerned and applied in chemical catalysis, medical materials, field sensing materials. Especially for gold and silver nano material, because of its optical and electrical properties? Small size effect, good stability and specific biological affinity, display it has high potential value, has become a hot research field. This paper designed the silver nano materials of four different methods for identification of specific amino acid, methionine and glutathione were established, the quantitative analysis method of histidine, the results of the study include the following aspects: (1) the establishment of methionine and methionine visualdetection inhibition of melamine based on the aggregation of gold nanoparticles induced. Under the optimized experimental conditions, using sodium citrate as reducing agent and stabilizer as the particle size of 13.0nm So, good dispersion of AuNPs sol. Melamine structure containing three amino groups, strong complexation with metal, so they through the ligand exchange interaction caused by the dispersion of gold nanoparticles into high aggregation and citrate anion gold nanoparticles, gold nanoparticles by the color of wine red gradually become purple and eventually become blue. Because of methionine and gold nanoparticles by both the N-Au and S-Au key combination, so with the addition of methionine solution, gradually inhibited the nano gold sol melamine induced aggregation solution gradually changed from blue to red wine, in order to achieve the target amino acid methionine fast, simple. The quantitative detection sensitivity. The sensing mechanism by TEM and nano particle size analyzer has been verified. The test results show that the uncorrected minimum detectable amount of methionine concentration was 0 .4 M, the quantitative analysis can be obtained in the 0.1-1.0 M within the scope of the theory of limit of detection by UV spectrum of (LOD) 24.5nM, this method was successfully applied to the detection of methionine in serum and urine, the average recovery rate was 95%-105%. (2) according to the inhibition of gold nanoparticles and design a aggregation rapid and sensitive methods for detection of glutathione.2.0 M 2- mercapto -1- methyl imidazole as aggregation agent can make obvious aggregation of gold nanoparticles, accompanied by the color changes from red to purple to blue.Cys in pH was 5.8 + 0.1 to AuNPs aggregation, color change from red to purple wine and for Hcy, when the pH is greater than 11, will cause the aggregation of AuNPs, but when the pH is in between the 5-7, will make AuNPs in a decentralized state, for GSH, when mixed with AuNPs, there are two carboxyl groups in pH is less than 4.5 and AuNPs particles with the GSH between Hydrogen bonding, AuNPs aggregation, when more than 4.5 pH, carboxyl groups due to deprotonation, AuNPs will not occur together. Therefore, changing the pH of the solution can effectively improve the selectivity of the method, the pH of the solution is adjusted to 5.8, Cys/AuNPs and Hcy/AuNPs will be aggregated, while GSH/AuNPs was still in a decentralized state the degree of aggregation. The gold nanoparticles decreased with the increase of the concentration of glutathione, gold nanoparticles gradually changed from blue to red wine, the minimum amount of glutathione detection visible for 0.1 M, quantitative analysis of low concentration by UV spectroscopy, glutathione concentration in the 0.1-1.0 M within the scope of the theoretical detection limit of detection 12 the nM. method has been successfully applied to human glutathione in blood and urine, the average recovery rate was 95%-103%. (3) glutathione induced inhibition of cysteine gold nanoparticles aggregation is established based on the Visual detection of glutathione. By the experimental detection of glutathione on a principle that, in the case of pH is 5.8, cystine, cysteine containing sulfhydryl compounds which could not be gathered or gathered and slight, cysteine can make the aggregation of gold nanoparticles, and with the increase of the concentration of cysteine. The nano gold color from red to purple wine with the size of.PH to determine whether the AuNPs aggregation and aggregation degree, therefore the selection of cysteine as aggregation agent, interestingly, glutathione and cysteine often due to similar structure but difficult to distinguish, and in this system, the design of the experiment itself can distinguish the two. When adding glutathione and with the continuous addition of glutathione, the color of the solution gradually from purple to red wine, so as to realize the quantitative detection and analysis of glutathione. The application of this method successfully In the detection of human glutathione in blood and urine, the average recovery rate was 90%-110%. (4) using modified sulfanilic acid nano silver (AgNPs) of histidine (His) by colorimetric detection. Under the optimized experimental conditions, using sodium borohydride reduction method for the synthesis of a size of about 6.7 nm dispersion SAA-AgNPs probe good. By TEM, the structure was characterized by infrared spectroscopy and UV spectroscopy, this experiment using histidine SAA-AgNPs sol induced aggregation, so as to achieve the purpose of quantitative detection of histidine. First of all, we found that His and SAA have imidazole ring, aromatic ring, we speculate that the imidazole ring and aromatic ring the PI pi bond accumulation will make SAA-AgNPs in a certain degree of aggregation, secondly, the electrostatic interaction between amino and carboxyl group on the His SAA is essential for the aggregation of SAA-AgNPs,, p-Aminobenzene Sulfonic The acid functional group and histidine as recognition by hydrogen bonding to silver nanoparticles occurred to some extent gathered. According to the above mechanism, with the increase of the concentration of histidine, nano silver color changed from light yellow to orange to purple, the color changes and UV absorption were achieved by qualitative and quantitative analysis of the optical spectra of histidine changes in 0-3.5 M within the scope of the detection limit is 52.7nM, the detection can be successfully applied to the actual samples of serum, serum sample recovery rate was 97%-107%.

【學(xué)位授予單位】：南昌大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB383.1;O657.3

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本文編號(hào)：1730621