【摘要】：表面增強拉曼技術(shù)(Surface-enhanced Raman spectroscopy,SERS)作為一種超靈敏分析技術(shù),具有快速、無損、不易淬滅以及水的干擾小等特點,在化學(xué)分析、生物診斷、以及環(huán)境監(jiān)測等領(lǐng)域收到了極大的關(guān)注。為獲取高質(zhì)SERS信號,需要使用具有高度靈敏性、均一性和重現(xiàn)性的SERS基底,基于貴金屬(Au、Ag)的微納米級結(jié)構(gòu)由于具有優(yōu)秀的SERS性能以及易于合成等優(yōu)勢被廣泛用于高效SERS基底的構(gòu)建。金納米星由于其表面尖銳枝角的存在,已被證明具有比球狀金納米顆粒更好的SERS活性。此外,基于金銀雙金屬的納米復(fù)合材料能夠有效結(jié)合單金屬納米材料優(yōu)良特性,也已經(jīng)證明能夠構(gòu)建高SERS活性基底。本論文的工作主要是通過二次種子介導(dǎo)生長法,將新制金納米星材料作為生長核,在其表面沉積銀層,繼續(xù)生長得到銀包金納米星材料。利用液滴蒸發(fā)自組裝法將所得銀包金納米星材料致密組裝在SMCSL超疏水層表面,制得含有高密度熱點分布的AuNS@Ag/SMCSL SERS基底,并利用該基底優(yōu)異的SERS檢測能力實現(xiàn)了人工尿液中6-TG的超靈敏檢測。具體工作內(nèi)容如下:1.采用二次種子介導(dǎo)生長法成功制備了一種銀包金納米星復(fù)合材料,并通過控制加入AgNO3溶液的濃度來調(diào)控金納米星表面的銀沉積量。分別利用透射電子顯微鏡(TEM)、能譜儀(EDS)、X射線粉末衍射(XRD)、掃描電子顯微鏡(SEM)等手段對產(chǎn)物的組成和微觀結(jié)構(gòu)進行了表征。以尼羅藍A為信號分子,對所制備AuNS@Ag的SERS性能進行了評估。結(jié)果表明:Ag的沉積明顯提高了AuNS@Ag的SERS性能,當(dāng)加入AgNO3濃度為5 mM時,AuNS@Ag具有最佳的SERS性能。2.基于液滴蒸發(fā)自組裝技術(shù)將已制得的AuNS@Ag納米顆粒組裝在SMCSL膜表面,制得含有高密度熱點的SERS基底。掃描電鏡圖和Raman圖證明星形納米顆粒致密組裝在SMCSL表面,產(chǎn)生高密度分布的熱點。已制得的AuNS@Ag/SMCSL基底展現(xiàn)相比AuNPs/SMCSL基底更高的SERS增強效果。此外,SERS基底對NBA的檢測濃度可降低至10-12M。模擬電場分布的結(jié)果證明,基于枝角狀A(yù)uNS@Ag納米顆粒的SERS基底具有更高的SERS增強能力。通過對實際分子鄰苯二胺和血紅蛋白的SERS檢測,證明該基底在痕量分析檢測領(lǐng)域具有很好的應(yīng)用前景。3.基于前期實驗制得的AuNS@Ag/SMCSL高效SERS基底,實現(xiàn)了不同環(huán)境中6-TG分子的超靈敏檢測。實驗將不同的6-TG溶液液滴直接滴在基底表面,并將AuNS@Ag聚集物完全包裹,達到浸泡的效果。利用SMCSL超疏水性質(zhì)能夠?qū)?-TG分子有效富集到SERS基底表面,從而大幅降低6-TG的濃度檢測限。通過檢測不同pH環(huán)境中的6-TG,可觀察pH對6-TG的SERS信號強度的影響。通過對不同共存干擾物質(zhì)環(huán)境中的6-TG進行SERS檢測,證明SERS檢測技術(shù)對6-TG具有高度選擇性。將所制得的SERS基底用于人工尿液環(huán)境中6-TG的檢測,分析了 SERS信號與6-TG濃度的關(guān)系,并確定了 6-TG的檢測濃度可降低至10-9 M。
[Abstract]:Surface enhanced Raman technique (Surface-enhanced Raman spectroscopy,SERS), as a hypersensitive analysis technique, has the advantages of fast, nondestructive, non-quenched and small water interference, etc., in chemical analysis, biological diagnosis, and so on. And environmental monitoring and other areas have received great attention. In order to obtain high quality SERS signals, a highly sensitive, uniform and reproducible SERS substrate based on precious metals (Au,) is needed. Ag) microstructures have been widely used in the construction of highly efficient SERS substrates due to their excellent SERS properties and easy synthesis. Gold nanoparticles have been proved to have better SERS activity than spherical gold nanoparticles due to the existence of sharp branching angles on the surface. In addition, the gold and silver bimetallic nanocomposites can effectively combine the excellent properties of monometallic nanomaterials and have been proved to be able to construct high SERS active substrates. The main work of this thesis is to use the new gold nanoparticles as the growth nucleus and deposit silver layer on the surface through the secondary seeding method to obtain the silver coated gold nanosars. The silver coated gold nanoparticles were assembled on the surface of SMCSL superhydrophobic layer by droplet evaporation self-assembly method, and the AuNS@Ag/SMCSL SERS substrate containing high density hot spots was prepared. The hypersensitive detection of 6-TG in artificial urine was realized by using the excellent SERS detection ability of the substrate. The specific contents of the work are as follows: 1. A silver clad gold nanocomposite was successfully prepared by secondary seeded growth method and the amount of silver deposition on the surface of gold nanocrystals was controlled by controlling the concentration of AgNO3 solution. The composition and microstructure of the product were characterized by transmission electron microscope (TEM),) (TEM), spectrometer (EDS), X ray powder diffraction (XRD), scanning electron microscope (SEM). The SERS properties of AuNS@Ag were evaluated using Nile blue A as signal molecule. The results show that the deposition of Ag improves the SERS performance of AuNS@Ag. When the concentration of AgNO3 is 5 mM, AuNS@Ag has the best SERS performance. The prepared AuNS@Ag nanoparticles were assembled on the surface of SMCSL films based on droplet evaporation self-assembly technology to prepare SERS substrates with high density hot spots. Scanning electron microscopy (SEM) and Raman images show that the starlike nanoparticles are tightly assembled on the surface of SMCSL, resulting in hot spots of high density distribution. The prepared AuNS@Ag/SMCSL substrate exhibits higher SERS enhancement than the AuNPs/SMCSL substrate. In addition, the detection concentration of NBA on SERS substrate can be reduced to 10-12M. The simulated electric field distribution shows that the SERS substrate based on dendritic AuNS@Ag nanoparticles has higher SERS enhancement ability. The SERS detection of the actual molecule o-phenylenediamine and hemoglobin shows that the substrate has a good application prospect in the field of trace analysis. The hypersensitive detection of 6-TG molecules in different environments was realized based on the AuNS@Ag/SMCSL SERS substrate prepared by previous experiments. In the experiment, the droplets of different 6-TG solutions were dripped directly on the substrate surface, and the AuNS@Ag aggregates were completely encapsulated to achieve the effect of soaking. By using the superhydrophobic properties of SMCSL, 6-TG molecules can be effectively enriched on the surface of SERS substrate, thus greatly reducing the detection limit of 6-TG concentration. The influence of pH on SERS signal intensity of 6-TG can be observed by detecting 6-TG in different pH environment. Through the SERS detection of 6-TG in the environment of different interference substances, it is proved that the SERS detection technology is highly selective to 6-TG. The SERS substrate was used to detect 6-TG in artificial urine environment. The relationship between the SERS signal and the concentration of 6-TG was analyzed, and the detection concentration of 6-TG could be reduced to 10-9 M.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.37

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