TWI464389B - Surface Enhancement Raman Spectroscopy Element and Its Manufacturing Method and Application - Google Patents
Surface Enhancement Raman Spectroscopy Element and Its Manufacturing Method and Application Download PDFInfo
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本發明是有關於一種表面增強拉曼光譜元件，特別是指一種不需乾燥待測樣品即可以測量的表面增強拉曼光譜元件。The present invention relates to a surface-enhanced Raman spectroscopy element, and more particularly to a surface-enhanced Raman spectroscopy element that can be measured without drying the sample to be tested.
表面增強拉曼散射(Surface-enhanced Raman Scattering，簡稱SERS)法於1974年被提出，係指當待測樣品放置在由奈米金屬顆粒或粒子簇(cluster)沉積形成的金屬表面時，待測樣品受金屬表面電漿共振產生之電磁場影響，能增強拉曼散射訊號至百萬倍以上之現象。SERS法被廣泛應用於製作表面增強拉曼基板，以利於後續用於分析微量樣品。The Surface-enhanced Raman Scattering (SERS) method was proposed in 1974 to refer to the sample to be tested when the sample to be tested is placed on a metal surface formed by deposition of nano metal particles or clusters. It is affected by the electromagnetic field generated by the resonance of the metal surface plasma, which can enhance the Raman scattering signal by more than one million times. The SERS method is widely used to fabricate surface-enhanced Raman substrates for subsequent analysis of trace samples.
在表面增強拉曼基板的製作方法中，銀鏡反應覆膜法因具備價格便宜且適於大量製備等優點，而成為主要製作方法。表面增強拉曼基板一般包含一金屬或玻璃板材，及一設置在該板材上且由銀或金所形成的奈米金屬粒子層。表面增強拉曼基板在使用時將基板浸入待測量溶液中或將待測溶液置於該基板表面上，以激發源(如雷射光源)直接照射該表面，並由偵測器收集散射光。In the method for producing a surface-enhanced Raman substrate, the silver mirror reaction coating method is mainly used because it has an advantage of being inexpensive and suitable for mass production. The surface-enhanced Raman substrate generally comprises a metal or glass plate, and a layer of nano metal particles disposed on the plate and formed of silver or gold. The surface-enhanced Raman substrate is immersed in the solution to be measured or the solution to be tested is placed on the surface of the substrate in use, and an excitation source (such as a laser source) directly illuminates the surface, and the scattered light is collected by the detector.
US2008/0291442揭示一種表面增強拉曼基板，製作方式是取一平面基板，先將多數個能夠偏極共振的奈米金屬粒子置於該基板上，再以高分子材料對該奈米金屬粒子進行固定，形成一覆蓋該基板並具有數個奈米金屬粒子鑲嵌 於其中的高分子層，且高分子層的表面有奈米金屬粒子露出。實際測量時，此一基板的配置方式有助於提升該奈米金屬粒子的穩定性，待測樣品可吸附於奈米金屬粒子露出於高分子層表面的部分，但對於測量低濃度或微量體積的待測樣品水溶液，則會因平面基板無法將待測樣品水溶液均勻侷限在一定區域中，致使待測樣品分佈不均的情況下，造成測量訊號缺乏再現性，難以進行定量量測。US 2008/0291442 discloses a surface-enhanced Raman substrate which is prepared by taking a planar substrate by first placing a plurality of nano metal particles capable of repolarization on the substrate, and then performing the nano metal particles with a polymer material. Fixed to form a substrate covering the substrate and having a plurality of nano metal particles inlaid The polymer layer is formed therein, and the surface of the polymer layer is exposed with nano metal particles. In actual measurement, the configuration of the substrate helps to improve the stability of the nano metal particles, and the sample to be tested can be adsorbed on the portion of the nano metal particles exposed on the surface of the polymer layer, but for measuring low concentration or micro volume. The aqueous solution of the sample to be tested may be limited to a certain area due to the inability of the planar substrate to uniformly limit the aqueous solution of the sample to be tested, resulting in a lack of reproducibility of the measurement signal and difficulty in quantitative measurement.
雖然文獻中有些學者嘗試以不同方法克服測量樣品水溶液的困擾，例如透過加熱去除水份，或設置包含親水性濾紙的基板，使待測樣品水溶液先與基板接觸後水再被濾去；這些方法還除了步驟繁瑣外，仍存有無法真正去除測量水份之疑慮，以及加熱後對奈米材料以及待測樣品水溶液之影響，或待測樣品水溶液在除水後對奈米金屬材料是否有足夠之吸附效果等問題。Although some scholars in the literature have tried to overcome the problem of measuring the aqueous solution of the sample by different methods, such as removing water by heating, or setting a substrate containing hydrophilic filter paper, the aqueous solution of the sample to be tested is first filtered after contact with the substrate; In addition to the cumbersome steps, there are still doubts that the water cannot be truly removed, and the effect on the nanomaterial and the aqueous solution to be tested after heating, or whether the aqueous solution of the sample to be tested is sufficient for the nano-metal material after water removal. Problems such as adsorption effect.
由上述可知，尋找一種對於測量低濃度或微量體積的待測樣品水溶液具有良好靈敏度及再現性的表面增強拉曼光譜元件，是目前重要的研究方向之一。From the above, it is known that a surface-enhanced Raman spectroscopy element having good sensitivity and reproducibility for measuring a low concentration or a small volume of an aqueous sample to be tested is one of the important research directions.
因此，本發明之第一目的，即在提供一種特別適用於量測待測樣品水溶液，且具有良好靈敏度及再現性的表面增強拉曼光譜元件。Accordingly, a first object of the present invention is to provide a surface-enhanced Raman spectroscopy element which is particularly suitable for measuring an aqueous solution of a sample to be tested and which has good sensitivity and reproducibility.
於是，本發明表面增強拉曼光譜元件，包含至少一具有一頂面的柱狀基材、至少一至少覆蓋該柱狀基材之頂面的疏水性高分子膜，及至少一形成於該頂面上並覆蓋該疏 水性高分子膜的奈米金屬粒子層。Therefore, the surface-enhanced Raman spectroscopy element of the present invention comprises at least one columnar substrate having a top surface, at least one hydrophobic polymer film covering at least a top surface of the columnar substrate, and at least one formed on the top Covering the surface A nano metal particle layer of a water-based polymer film.
本發明之第二目的，在於提供一種表面增強拉曼光譜元件的製造方法，包含：提供至少一柱狀基材，係具有一頂面；設置至少一疏水性高分子膜，係至少覆蓋該柱狀基材之頂面；及形成至少一奈米金屬粒子層，係位於該頂面上並覆蓋該疏水性高分子膜。A second object of the present invention is to provide a method for fabricating a surface-enhanced Raman spectroscopy element, comprising: providing at least one columnar substrate having a top surface; and providing at least one hydrophobic polymer film covering at least the column a top surface of the substrate; and a layer of at least one nano metal particle formed on the top surface and covering the hydrophobic polymer film.
本發明之第三目的，在於提供一種拉曼儀器，包含：(a)一輻射源、(b)一拉曼感應器，包括至少一如前所述之表面增強拉曼光譜元件，及(c)一偵測器。A third object of the present invention is to provide a Raman apparatus comprising: (a) a radiation source, (b) a Raman sensor comprising at least one surface-enhanced Raman spectroscopy element as previously described, and (c ) a detector.
一般平面式的表面增強拉曼光譜元件測量時，待測樣品的擴散方向和擴散範圍不易掌控且無法均勻覆蓋於該平面式基板上，且當待測樣品為水溶液時特別難以準確地進行定量分析。為了解決上述問題，本發明透過該表面增強拉曼光譜元件呈柱狀結構以及疏水性高分子膜的設置，使得待測樣品得以限制在該形成於頂面上的奈米金屬粒子層上，而達到能夠準確測量微量體積之樣品的目的。值得一提的是，當待測樣品為水溶液時，更可藉由疏水性高分子膜的設置並運用水固有的表面張力，使得樣品能夠以液滴型態集中於該奈米金屬粒子層上而不散去；因此，運用本發明表面增強拉曼元件不需再進行除水處理即可以直接測量，並且能夠測量微量體積的待測樣品水溶液，更可明顯提昇靈敏度、再現性以及量測效率，大幅地改善了過去量測待測樣品水溶液的問題。When the planar surface-enhanced Raman spectroscopy element is generally measured, the diffusion direction and diffusion range of the sample to be tested are difficult to control and cannot be uniformly covered on the planar substrate, and it is particularly difficult to accurately perform quantitative analysis when the sample to be tested is an aqueous solution. . In order to solve the above problems, the present invention provides a columnar structure and a hydrophobic polymer film through the surface-enhanced Raman spectroscopy element, so that the sample to be tested is confined on the nano metal particle layer formed on the top surface, and Achieve the purpose of accurately measuring a small volume of sample. It is worth mentioning that when the sample to be tested is an aqueous solution, the sample can be concentrated on the nano metal particle layer in a droplet pattern by the arrangement of the hydrophobic polymer film and using the surface tension inherent to the water. Therefore, the surface-enhanced Raman element of the present invention can be directly measured without using water removal treatment, and can measure a small volume of the sample aqueous solution to be tested, and can significantly improve sensitivity, reproducibility, and measurement efficiency. , greatly improved the problem of measuring the aqueous solution of the sample to be tested in the past.
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之三個較佳具體例的詳細說明中，將可清楚的呈現。The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.
在本發明被詳細描述之前，要注意的是，在以下的說明內容中，類似的元件是以相同的編號來表示。Before the present invention is described in detail, it is noted that in the following description, similar elements are denoted by the same reference numerals.
如圖1所示，本發明表面增強拉曼光譜元件之第一較佳具體例，包含：至少一柱狀基材1，係具有一頂面11；至少一疏水性高分子膜2，係至少覆蓋該柱狀基材1之頂面11；及至少一奈米金屬粒子層3，係形成於該頂面1上並覆蓋該疏水性高分子膜2。As shown in FIG. 1, a first preferred embodiment of the surface-enhanced Raman spectroscopy element of the present invention comprises: at least one columnar substrate 1 having a top surface 11; at least one hydrophobic polymer film 2, at least The top surface 11 of the columnar substrate 1 is covered; and at least one nano metal particle layer 3 is formed on the top surface 1 and covers the hydrophobic polymer film 2.
該頂面11的形狀並沒有特別限制；較佳地，該頂面11的面積為0.01至10 mm2 ，透過使待測樣品集中於特定面積的範圍上，能有效增加該元件的再現性。更佳地，該頂面11的面積為0.5至3.5 mm2 。The shape of the top surface 11 is not particularly limited; preferably, the top surface 11 has an area of 0.01 to 10 mm 2 , and the reproducibility of the element can be effectively increased by concentrating the sample to be tested on a specific area. More preferably, the top surface 11 has an area of 0.5 to 3.5 mm 2 .
該柱狀基材1的材料並無特別限制，只要能使該疏水性高分子膜2確實覆蓋於其上即可。較佳地，該柱狀基材1是由選自於下列所構成群組之材料所製成：高分子、石英、玻璃及金屬。又較佳地，該柱狀基材1是由高分子材料所組成。更佳地，製成該柱狀基材1的材料是聚甲基丙烯酸甲酯(polymethylmethacrylate，簡稱PMMA)，例如使用PMMA塑膠光纖(PMMA plastic optical fiber)。The material of the columnar substrate 1 is not particularly limited as long as the hydrophobic polymer film 2 can be surely covered thereon. Preferably, the columnar substrate 1 is made of a material selected from the group consisting of a polymer, quartz, glass, and metal. Further preferably, the columnar substrate 1 is composed of a polymer material. More preferably, the material of the columnar substrate 1 is polymethylmethacrylate (PMMA), for example, PMMA plastic optical fiber.
較佳地，該疏水性高分子膜2具有一個粗糙表面(圖未示)。相較於平滑表面，奈米金屬粒子較易附著於粗糙表面上，且表面越粗糙，接觸面積越大，附著量也越多；而奈 米金屬粒子的含量越多，有助提升該表面增強拉曼光譜元件的靈敏度。更佳地，該疏水性高分子膜2還具有多數個孔隙(圖未示)，當奈米金屬粒子深入至該等孔隙中，可使該元件的靈敏度更提升。Preferably, the hydrophobic polymer film 2 has a rough surface (not shown). Compared with the smooth surface, the nano metal particles are more likely to adhere to the rough surface, and the rougher the surface, the larger the contact area, the more the adhesion; The higher the content of the metal particles, the better the sensitivity of the surface-enhanced Raman spectroscopy element. More preferably, the hydrophobic polymer film 2 also has a plurality of pores (not shown), and when the nano metal particles penetrate into the pores, the sensitivity of the element is further improved.
較佳地，該疏水性高分子膜2是由具備還原力的疏水性高分子所組成；所謂「還原力」是指該高分子本身具有提供電子的能力，或該高分子經由吸附或溶解於可提供電子的有機溶劑而具有還原力；該可提供電子的有機溶劑可例如但不限於：二甲基甲醯胺(N,N-Dimethylformamide，簡稱DMF)、二甲亞碸(Dimethyl sulfoxide，簡稱DMSO)、丙酮(Acetone)，及四氫呋喃(Tetrahydrofuran,THF)。又較佳地，該疏水性高分子膜2是由至少一種選自於由下列所構成群組的疏水性高分子所形成：聚偏二氟乙烯(polyvinylidenefluoride，簡稱PVDF)、聚乙烯、聚丙烯、聚醯胺(Polyamide)、聚苯乙烯(polystyrene，簡稱PS)、聚碳酸酯(polycarbonate，簡稱PC)，及PMMA。更佳地，該疏水性高分子膜2是聚偏二氟乙烯、聚苯乙烯、聚碳酸酯，及PMMA。Preferably, the hydrophobic polymer film 2 is composed of a hydrophobic polymer having a reducing power; the term "reducing power" means that the polymer itself has the ability to supply electrons, or the polymer is adsorbed or dissolved. An electron organic solvent may be provided to have a reducing power; the organic solvent capable of providing electrons may be, for example but not limited to, N,N-Dimethylformamide (DMF), Dimethyl sulfoxide (abbreviation). DMSO), acetone (Acetone), and tetrahydrofuran (THF). Further preferably, the hydrophobic polymer film 2 is formed of at least one hydrophobic polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polyethylene, and polypropylene. , Polyamide, polystyrene (PS), polycarbonate (PC), and PMMA. More preferably, the hydrophobic polymer film 2 is polyvinylidene fluoride, polystyrene, polycarbonate, and PMMA.
本發明表面增強拉曼光譜元件之第二較佳具體例係如圖2所示，其與第一較佳具體例的不同之處在於該疏水性高分子膜2包覆該柱狀基材1之一端，使該疏水性高分子膜2除覆蓋該柱狀基材1的頂面11外，更覆蓋由該頂面11向下延伸之部份柱狀基材1側壁。透過上述設置，再加上奈米金屬粒子層3僅形成於頂面11上，更有助於使待測之 樣品水溶液更集中於該表面增強拉曼光譜元件之頂面11。A second preferred embodiment of the surface-enhanced Raman spectroscopy element of the present invention is shown in FIG. 2, which is different from the first preferred embodiment in that the hydrophobic polymer film 2 covers the columnar substrate 1 At one end, the hydrophobic polymer film 2 covers the side wall of the columnar substrate 1 extending downward from the top surface 11 in addition to the top surface 11 of the columnar substrate 1. Through the above arrangement, the nano metal particle layer 3 is formed only on the top surface 11, which is more helpful for the test to be tested. The aqueous sample solution is more concentrated on the top surface 11 of the surface enhanced Raman spectroscopy element.
該奈米金屬粒子層3是透過沉澱或吸附作用而覆蓋於該疏水性高分子膜2上，如圖3所示。較佳地，該奈米金屬粒子層3是由至少一選自於下列所構成群組之奈米金屬粒子所形成：金、銀及鉑。更佳地，該奈米金屬粒子層3是由銀所形成。The nano metal particle layer 3 is coated on the hydrophobic polymer film 2 by precipitation or adsorption, as shown in FIG. Preferably, the nano metal particle layer 3 is formed of at least one nano metal particle selected from the group consisting of gold, silver and platinum. More preferably, the nano metal particle layer 3 is formed of silver.
較佳地，該奈米金屬粒子的粒徑範圍為10至200 nm；更佳地，該奈米金屬粒子的粒徑為100 nm。Preferably, the nano metal particles have a particle size ranging from 10 to 200 nm; more preferably, the nano metal particles have a particle diameter of 100 nm.
此外，本發明量測體積小至0.5μL的待測樣品，仍具有良好靈敏度。當待測樣品體積較大時，將該基材沾取代測樣品即可以進行測量。In addition, the present invention measures a sample having a volume as small as 0.5 μL and still has good sensitivity. When the volume of the sample to be tested is large, the substrate can be measured by measuring the sample.
如圖4所示，本發明表面增強拉曼光譜元件之第三較佳具體例包含：複數個柱狀基材1，每一柱狀基材1係彼此平行間隔排列，且該等柱狀基材1之頂面11共同形成一水平面。更佳地，在該等柱狀基材1中，每一柱狀基材1係彼此平行間隔排列地並設置於一承載板上(圖未示)。該承載板的材質沒有特別限定，只要能緊密固定該等柱狀基材即可；該承載板可例如但不限於：鋁板、鐵板、不銹鋼板、壓克力板、聚乙烯板，或聚丙烯板。As shown in FIG. 4, a third preferred embodiment of the surface-enhanced Raman spectroscopy element of the present invention comprises: a plurality of columnar substrates 1, each of which is arranged in parallel with each other, and the columnar groups are arranged The top surfaces 11 of the material 1 together form a horizontal plane. More preferably, in the columnar substrates 1, each of the columnar substrates 1 is arranged in parallel with each other and disposed on a carrier plate (not shown). The material of the carrier plate is not particularly limited as long as the columnar substrates can be tightly fixed; the carrier plate can be, for example but not limited to: aluminum plate, iron plate, stainless steel plate, acrylic plate, polyethylene plate, or poly Acrylic board.
本發明表面增強拉曼光譜元件的製造方法，包含：提供至少一柱狀基材，係具有一頂面；設置至少一疏水性高分子膜，係至少覆蓋該柱狀基材之頂面；及形成至少一奈米金屬粒子層，係位於該頂面上並覆蓋該疏水性高分子膜。The method for manufacturing a surface-enhanced Raman spectroscopy element of the present invention comprises: providing at least one columnar substrate having a top surface; and providing at least one hydrophobic polymer film covering at least a top surface of the columnar substrate; A layer of at least one nano metal particle is formed on the top surface and covers the hydrophobic polymer film.
該表面增強拉曼光譜元件的規格及材料與前述相同，在此不再贅述。The specifications and materials of the surface-enhanced Raman spectroscopy element are the same as those described above, and are not described herein again.
較佳地，該頂面的面積為0.01至10 mm2 。Preferably, the top surface has an area of 0.01 to 10 mm 2 .
較佳地，該疏水性高分子膜是由至少一選自於由下列所構成群組的疏水性高分子所形成：聚偏二氟乙烯、聚乙烯、聚丙烯、聚醯胺、聚苯乙烯、聚碳酸酯，及聚甲基丙烯酸甲酯。Preferably, the hydrophobic polymer film is formed of at least one hydrophobic polymer selected from the group consisting of polyvinylidene fluoride, polyethylene, polypropylene, polyamine, polystyrene. , polycarbonate, and polymethyl methacrylate.
該疏水性高分子膜的製作方法並沒有特別限制。較佳地是至少將該柱狀基材之頂面沾取或浸入一由疏水性高分子及溶劑所構成之疏水性高分子溶液中，取出並進行乾燥，即可以形成覆蓋於該基材頂面的疏水性高分子膜。於乾燥期間，疏水性高分子發生自聚作用，會使疏水性高分子與溶劑分離，更有助於該疏水性高分子膜形成粗糙表面及孔隙。更佳地，乾燥時間為5至10分鐘，其目的在於使疏水性高分子溶液的溶劑尚未完全乾燥，而該疏水性高分子膜也已經成形。The method for producing the hydrophobic polymer film is not particularly limited. Preferably, at least the top surface of the columnar substrate is dipped or immersed in a hydrophobic polymer solution composed of a hydrophobic polymer and a solvent, and taken out and dried to form a top of the substrate. Hydrophobic polymer film on the surface. During the drying, the hydrophobic polymer undergoes self-polymerization, which separates the hydrophobic polymer from the solvent, and contributes to the formation of a rough surface and pores of the hydrophobic polymer film. More preferably, the drying time is 5 to 10 minutes, and the purpose is to make the solvent of the hydrophobic polymer solution not completely dried, and the hydrophobic polymer film has also been formed.
特別值得一提的是，上述之乾燥步驟無需讓疏水性高分子膜上的溶劑完全去除，因為殘留的溶劑於製作奈米金屬粒子層時有助於使更多奈米金屬粒子形成並覆蓋該疏水性高分子膜，使該元件的靈敏度提升；特別是殘留於疏水性高分子膜孔隙中的溶劑，有助於使該奈米金屬粒子深入地形成於該孔隙中。It is particularly worth mentioning that the above drying step does not require complete removal of the solvent on the hydrophobic polymer film because the residual solvent helps to form and cover more nano metal particles when the nano metal particle layer is formed. The hydrophobic polymer film enhances the sensitivity of the element; in particular, the solvent remaining in the pores of the hydrophobic polymer film helps to form the nano metal particles deeply in the pore.
較佳地，該疏水性高分子溶液的濃度為1至25%(w/v)。更佳地為15%(w/v)。Preferably, the concentration of the hydrophobic polymer solution is from 1 to 25% (w/v). More preferably 15% (w/v).
構成該疏水性高分子溶液的溶劑係依據所使用之疏水性高分子來選擇，可例如但不限於：二甲基甲醯胺、二甲亞碸、丙酮、甲苯(Toluene)，或四氫呋喃。The solvent constituting the hydrophobic polymer solution is selected depending on the hydrophobic polymer to be used, and may be, for example but not limited to, dimethylformamide, dimethyl hydrazine, acetone, toluene, or tetrahydrofuran.
當該柱狀基材為聚甲基丙烯酸甲酯，形成該疏水性高分子膜的另一種方法可例如對該基材之頂面進行一表面處理，使形成一疏水性高分子膜。具體的作法是至少將該柱狀基材之頂面浸泡於一表面處理液中。When the columnar substrate is polymethyl methacrylate, another method of forming the hydrophobic polymer film may, for example, subject a top surface of the substrate to a surface treatment to form a hydrophobic polymer film. Specifically, at least the top surface of the columnar substrate is immersed in a surface treatment liquid.
較佳地，該表面處理液是選自於：乙二胺(ethylenediamine)-二甲亞碸溶液、硫酸水溶液、氫氧化鈉水溶液，及乙胺(ethylamine)水溶液。較佳地，該表面處理液的濃度為0.1至4M。更佳地，該表面處理液為1M的乙二胺-二甲亞碸溶液，或先浸泡乙二胺-二甲亞碸溶液再浸泡乙胺水溶液。Preferably, the surface treatment liquid is selected from the group consisting of ethylenediamine-dimethyl hydrazine solution, aqueous sulfuric acid solution, aqueous sodium hydroxide solution, and aqueous solution of ethylamine. Preferably, the surface treatment liquid has a concentration of 0.1 to 4M. More preferably, the surface treatment solution is a 1 M solution of ethylenediamine-dimethylhydrazine, or the ethylenediamine-dimethylidene solution is first soaked and the aqueous solution of ethylamine is immersed.
較佳地，該表面處理的時間為5至60分鐘，更佳地為45分鐘。Preferably, the surface treatment time is from 5 to 60 minutes, more preferably 45 minutes.
該奈米金屬粒子層的形成方法並沒有特別限制，只要使該奈米金屬粒子層能夠形成於該頂面上並覆蓋該疏水性高分子膜即可，可例如但不限於各種已知的作法，例如：電化學粗糙電極法、金屬膠體製備覆膜法、氣相沉積金屬島製備法、化學侵蝕法、金屬鉗入膠膜法、銀鏡反應覆膜法、以及光阻或電子束製程。較佳地，該奈米金屬粒子層是利用低成本且適於大量製造的銀鏡反應覆膜法來形成。The method for forming the nano metal particle layer is not particularly limited as long as the nano metal particle layer can be formed on the top surface and covers the hydrophobic polymer film, and may be, for example but not limited to, various known methods. For example, electrochemical rough electrode method, metal colloid preparation film method, vapor deposition metal island preparation method, chemical etching method, metal clamp film method, silver mirror reaction film method, and photoresist or electron beam process. Preferably, the nano metal particle layer is formed by a silver mirror reaction coating method which is low in cost and suitable for mass production.
其中，運用銀鏡反應覆膜法的具體作法可例如但不限於：提供一銀氨溶液，將覆蓋有該疏水性高分子膜的基材 頂面浸入該銀氨溶液中，並加入作為還原劑的葡萄糖溶液，使奈米銀粒子形成於該疏水性高分子膜上。此時，若銀氨溶液與殘留於疏水性高分子膜的溶劑接觸，有助於使奈米銀粒子還原。The specific method of using the silver mirror reaction coating method may be, for example but not limited to, providing a silver ammonia solution, and the substrate covered with the hydrophobic polymer film. The top surface is immersed in the silver ammonia solution, and a glucose solution as a reducing agent is added to form nano silver particles on the hydrophobic polymer film. At this time, if the silver ammonia solution is brought into contact with the solvent remaining in the hydrophobic polymer film, it contributes to reduction of the nano silver particles.
較佳地，該葡萄糖溶液的濃度為0.1至2M，更佳地為0.25至0.5M；較佳地，反應溫度為50至80℃；較佳地，反應時間為2至20分鐘。Preferably, the concentration of the glucose solution is from 0.1 to 2 M, more preferably from 0.25 to 0.5 M; preferably, the reaction temperature is from 50 to 80 ° C; preferably, the reaction time is from 2 to 20 minutes.
本發明拉曼儀器，包含(a)一輻射源；(b)一拉曼感應器，包括至少一如前所述之表面增強拉曼光譜元件；及(c)一偵測器。使用該拉曼儀器時，首先將待測樣品沾附於該表面增強拉曼光譜元件；該拉曼感應器由下方被該輻射源照射，使該奈米金屬粒子層產生電漿場，電漿場與待測樣品的分子耦合產生拉曼光子，該偵測器偵測到拉曼光子並收集資料，以能量函數呈現，產生待測樣品特有的光譜。本發明所屬技術領域中具有通常知識者應能夠選擇恰當的單色雷射光的波長，以符合所使用之奈米金屬粒子之光學常數，藉此最佳化產生的電漿場。The Raman apparatus of the present invention comprises (a) a radiation source; (b) a Raman sensor comprising at least one surface-enhanced Raman spectroscopy element as previously described; and (c) a detector. When the Raman instrument is used, the sample to be tested is first adhered to the surface-enhanced Raman spectroscopy element; the Raman sensor is irradiated by the radiation source from below, so that the nano metal particle layer generates a plasma field, and the plasma The molecular coupling of the field with the sample to be tested produces a Raman photon that detects Raman photons and collects the data, presenting it as an energy function, producing a spectrum specific to the sample to be tested. Those of ordinary skill in the art to which the present invention pertains should be able to select the appropriate wavelength of the monochromatic laser light to conform to the optical constants of the nano metal particles used, thereby optimizing the resulting plasma field.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
取PMMA光纖(呈圓柱狀，直徑為2 mm，長為1.5 cm)作為柱狀基板，將該柱狀基板浸入15%(w/v)聚偏二氟乙烯- 二甲基甲醯胺溶液(以下簡稱PVDF-DMF溶液)後取出，使該柱狀基材之一端沾附有疏水性高分子溶液。A PMMA fiber (in a cylindrical shape, 2 mm in diameter and 1.5 cm in length) was used as a columnar substrate, and the columnar substrate was immersed in 15% (w/v) polyvinylidene fluoride- The dimethylformamide solution (hereinafter referred to as PVDF-DMF solution) is taken out, and one end of the columnar substrate is adhered with a hydrophobic polymer solution.
待該柱狀基材乾燥10分鐘後，浸入一由5 mL 15mM硝酸銀溶液與1.5 mL 0.5M葡萄糖配製的銀氨溶液進行銀鏡反應28分鐘，之後取出並以去離子水浸泡清洗後乾燥儲存，製得實施例1的表面增強拉曼光譜元件。實施例1之材料及規格記載於表1。After the columnar substrate was dried for 10 minutes, it was immersed in a silver ammonia solution prepared by 5 mL of 15 mM silver nitrate solution and 1.5 mL of 0.5 M glucose for 28 minutes, then taken out, washed with deionized water, dried, and stored. The surface-enhanced Raman spectroscopy element of Example 1 was obtained. The materials and specifications of Example 1 are shown in Table 1.
實施例2及3之作法大致與實施例1相同，不同之處在於改變該柱狀基材之直徑分別為0.5 mm及1 mm。實施例2及3之材料及規格記載於表1。The operations of Examples 2 and 3 were substantially the same as those of Example 1, except that the diameter of the columnar substrate was changed to 0.5 mm and 1 mm, respectively. The materials and specifications of Examples 2 and 3 are shown in Table 1.
取PMMA光纖(呈圓柱狀，直徑為2 mm，長為1.5 cm)作為柱狀基板，將該柱狀基板浸入15%(w/v)聚苯乙烯-DMF溶液(以下簡稱PS-DMF溶液)後取出，使該柱狀基材之一端沾附有疏水性高分子溶液。A PMMA fiber (in a cylindrical shape, 2 mm in diameter and 1.5 cm in length) was used as a columnar substrate, and the columnar substrate was immersed in a 15% (w/v) polystyrene-DMF solution (hereinafter referred to as PS-DMF solution). After that, it is taken out so that one end of the columnar substrate is adhered with a hydrophobic polymer solution.
待該柱狀基材乾燥10分鐘後，該柱狀基材之一端被疏水性高分子膜覆蓋，浸入DMF中後取出，再浸入一由5 mL 15mM硝酸銀溶液與1.5 mL 0.5M葡萄糖配製的銀氨溶液進行銀鏡反應28分鐘，之後取出並以去離子水浸泡清洗後乾燥儲存，製得實施例4的表面增強拉曼光譜元件。實施例4之材料及規格記載於表1。After the columnar substrate was dried for 10 minutes, one end of the columnar substrate was covered with a hydrophobic polymer film, immersed in DMF, and then taken out, and then immersed in a silver powder prepared from 5 mL of 15 mM silver nitrate solution and 1.5 mL of 0.5 M glucose. The ammonia solution was subjected to a silver mirror reaction for 28 minutes, and then taken out, washed with deionized water, and then dried and stored to obtain a surface-enhanced Raman spectrum element of Example 4. The materials and specifications of Example 4 are shown in Table 1.
實施例5及6之作法大致與實施例4相同，不同之處 在於改變該疏水性高分子溶液，分別為1%(w/V)聚碳酸酯-四氫呋喃溶液(簡稱PC-THF溶液)及1.5%(w/v)聚甲基丙烯酸甲酯-甲苯溶液(簡稱PMMA-Toluene溶液)。實施例5及6之材質及規格記載於表1。The practices of Embodiments 5 and 6 are substantially the same as those of Embodiment 4, and the differences are the same. In order to change the hydrophobic polymer solution, respectively, 1% (w / V) polycarbonate - tetrahydrofuran solution (referred to as PC-THF solution) and 1.5% (w / v) polymethyl methacrylate - toluene solution (referred to as PMMA-Toluene solution). The materials and specifications of Examples 5 and 6 are shown in Table 1.
實施例7及8之作法大致與實施例1相同，不同之處在於改變該柱狀基材之材料，分別為石英及玻璃。實施例7及8之材質及規格記載於表1。The operations of Examples 7 and 8 were substantially the same as those of Example 1, except that the materials of the columnar substrate were changed to be quartz and glass, respectively. The materials and specifications of Examples 7 and 8 are shown in Table 1.
取一鋁板，以電鑽鑽孔，以於鋁板上形成數個彼此間隔排列的孔洞。將數個實施例1製備之表面增強拉曼光譜元件分別置入孔洞中並固定，調整該等元件的頂面共同形成一水平面，製得如圖5所示之表面增強拉曼光譜元件。An aluminum plate is taken and drilled with an electric drill to form a plurality of holes arranged at intervals on the aluminum plate. A plurality of surface-enhanced Raman spectroscopy elements prepared in Example 1 were respectively placed in holes and fixed, and the top surfaces of the elements were adjusted to form a horizontal plane to obtain a surface-enhanced Raman spectroscopy element as shown in FIG.
取一玻璃基板(長2.5 cm，寬2.5 cm)作為平面基板，不設置任何疏水性高分子膜，直接將該平面基板之一面浸入一由5 mL 15mM硝酸銀溶液與1.5 mL 0.5M葡萄糖配製的銀氨溶液進行銀鏡反應28分鐘，之後取出並以去離子水浸泡清洗後乾燥儲存，製得比較例1的表面增強拉曼光譜板。比較例1之材質及規格記載於表1。Take a glass substrate (length 2.5 cm, width 2.5 cm) as a flat substrate, without any hydrophobic polymer film, directly immerse one side of the planar substrate into a silver prepared from 5 mL of 15 mM silver nitrate solution and 1.5 mL of 0.5 M glucose. The ammonia solution was subjected to a silver mirror reaction for 28 minutes, and then taken out, washed with deionized water, and then dried, and a surface-enhanced Raman spectrum plate of Comparative Example 1 was obtained. The materials and specifications of Comparative Example 1 are shown in Table 1.
比較例2之作法大致與比較例1相同，皆不設置疏水性高分子膜，不同之處在於該平面基板之材質為PMMA。 比較例2之材質及規格記載於表1。The procedure of Comparative Example 2 was substantially the same as that of Comparative Example 1, and no hydrophobic polymer film was provided, except that the material of the planar substrate was PMMA. The materials and specifications of Comparative Example 2 are shown in Table 1.
測試例1是取實施例1製備之表面增強拉曼光譜元件結合拉曼儀器分別對待測樣品進行測量，測試方法是將該表面增強拉曼光譜元件浸泡於10 ppm對胺苯硫酚(para-aminothiophenol，簡稱pATP)甲醇溶液中30分鐘，使該待測樣品吸附於該奈米金屬粒子層後，以632.8 nm進行測量。In Test Example 1, the surface-enhanced Raman spectroscopy element prepared in Example 1 was measured in combination with a Raman instrument, and the surface-enhanced Raman spectroscopy element was immersed in 10 ppm of thiophenol (para-). The aminothiophenol (pATP) was used for 30 minutes in a methanol solution, and the sample to be tested was adsorbed to the nano metal particle layer, and then measured at 632.8 nm.
測試例1之待測樣品的種類、體積、濃度範圍及測試條件記載於表2，測試結果請參見表2所記載之對應圖式。The type, volume, concentration range and test conditions of the sample to be tested in Test Example 1 are shown in Table 2. For the test results, refer to the corresponding patterns in Table 2.
測試例2、5至8及11是取實施例1製備之表面增強拉曼光譜元件結合拉曼儀器分別對待測樣品進行測量，測試方法是分別將該等待測樣品直接滴於實施例1表面增強拉曼光譜元件之奈米金屬粒子層，並以632.8 nm進行測量。Test Examples 2, 5 to 8 and 11 are obtained by taking the surface-enhanced Raman spectroscopy element prepared in Example 1 in combination with the Raman instrument to measure the sample to be tested. The test method is to directly drop the sample to be tested on the surface enhancement of Example 1 A layer of nano metal particles of a Raman spectroscopy element and measured at 632.8 nm.
測試例2、5至8及11之待測樣品的種類、體積、濃度範圍及測試條件記載於表2，測試結果請參見表2所記載之對應圖式。The types, volumes, concentration ranges and test conditions of the samples to be tested in Test Examples 2, 5 to 8 and 11 are shown in Table 2. For the test results, refer to the corresponding patterns in Table 2.
測試例3、9、10及12是以不同濃度的待測樣品對該表面增強拉曼光譜元件進行動態範圍研究。Test Examples 3, 9, 10 and 12 were conducted on the dynamic range of the surface-enhanced Raman spectroscopy element with different concentrations of the sample to be tested.
測試例3、9、10及12之待測樣品的種類、體積、濃度範圍及測試條件記載於表2，測試結果請參見表2所記載之對應圖式。The types, volumes, concentration ranges and test conditions of the samples to be tested in Test Examples 3, 9, 10 and 12 are shown in Table 2. For the test results, see the corresponding diagrams in Table 2.
測試例4是以不同體積的待測樣品對該表面增強拉曼光譜元件進行研究，觀察該表面增強拉曼光譜元件量測微量體積之待測樣品的靈敏度。In Test Example 4, the surface-enhanced Raman spectroscopy element was studied with different volumes of the sample to be tested, and the sensitivity of the surface-enhanced Raman spectroscopy element for measuring the micro-volume of the sample to be tested was observed.
測試例4之待測樣品種類、體積範圍、濃度範圍及測試條件記載於表2，測試結果請參見表2所記載之對應圖式。The type, volume range, concentration range and test conditions of the sample to be tested in Test Example 4 are shown in Table 2. For the test results, please refer to the corresponding drawings in Table 2.
測試例13至22是取實施例製備之表面增強拉曼光譜元件結合拉曼儀器對待測樣品進行測量，測試方法是將待測水溶液樣品直接滴於表面增強拉曼光譜元件之奈米金屬粒子層後進行測量，或是透過浸泡於待測樣品中30分鐘使待測樣品吸附於表面增強拉曼光譜元件之奈米金屬粒子層後進行測量。Test Examples 13 to 22 are obtained by taking the surface-enhanced Raman spectroscopy element prepared in the embodiment in combination with the sample to be tested by the Raman instrument by directly dropping the sample of the aqueous solution to be tested on the nano-metal layer of the surface-enhanced Raman spectroscopy element. The measurement is performed after the measurement, or the sample to be tested is adsorbed to the nano metal particle layer of the surface-enhanced Raman spectroscopy element by immersing in the sample to be tested for 30 minutes.
測試例13至22所用之表面增強拉曼光譜元件，待測樣品的種類、體積、濃度範圍及測試條件記載於表2，測試結果請參見表2所記載之對應圖式。The surface-enhanced Raman spectroscopy elements used in Test Examples 13 to 22, the type, volume, concentration range and test conditions of the sample to be tested are shown in Table 2. For the test results, refer to the corresponding patterns in Table 2.
測試比較例1至4是取比較例1及2製備之平面式的表面增強拉曼光譜元件結合拉曼儀器對待測樣品進行，測量測試方法是將待測水溶液樣品直接滴於表面增強拉曼光譜元件之奈米金屬粒子層後進行測量，或是透過浸泡於待測樣品中30分鐘，使待測樣品吸附於表面增強拉曼光譜元件之奈米金屬粒子層後進行測量。Test Comparative Examples 1 to 4 were prepared by using the planar surface-enhanced Raman spectroscopy element prepared in Comparative Examples 1 and 2 in combination with the sample to be tested by the Raman instrument. The measurement test method was to directly drop the sample of the aqueous solution to be tested on the surface-enhanced Raman spectroscopy. The nano metal particle layer of the device is measured or immersed in the sample to be tested for 30 minutes, and the sample to be tested is adsorbed to the nano metal particle layer of the surface-enhanced Raman spectroscopy element for measurement.
測試比較例1至4所用之表面增強拉曼光譜元件，待測樣品的種類、體積、濃度範圍及測試條件記載於表2，測試結果請參見表2所記載之對應圖式。The surface-enhanced Raman spectroscopy elements used in Comparative Examples 1 to 4 were tested. The type, volume, concentration range and test conditions of the samples to be tested are shown in Table 2. For the test results, refer to the corresponding patterns in Table 2.
圖6之(a)顯示測試例1之圖譜。圖6之(b)與(c)分別為測量0.4%(w/v)pATP丙酮溶液與0.4%(w/v)pATP甲醇溶液之拉曼光譜圖；(d)為測量固態pATP所得之光譜圖，其中(b)、(c)及(d)光譜圖皆是以無表面增強效果的拉曼光譜儀器測量，待測樣品的濃度明顯高於測試例1之待測樣品的濃度10 ppm，且光譜圖的雜訊較多。比較(a)光譜圖與(b)或(c)光譜圖，本發明的增強效應達107 倍。(a) of Fig. 6 shows a map of Test Example 1. (b) and (c) of Figure 6 are Raman spectra of 0.4% (w/v) pATP acetone solution and 0.4% (w/v) pATP methanol solution, respectively; (d) spectra obtained by measuring solid pATP In the figure, the (b), (c) and (d) spectra are measured by Raman spectroscopy without surface enhancement. The concentration of the sample to be tested is significantly higher than the concentration of the sample to be tested in Test Example 1 by 10 ppm. And there are more noises in the spectrum. Comparing (a) the spectrogram with the (b) or (c) spectrogram, the enhancement effect of the present invention is 10 7 times.
圖7之(a)顯示測試例2之光譜圖；(b)為無表面增強效果的拉曼光譜儀器測量固態純苯甲酸之光譜圖，比較(a)光譜圖與(b)光譜圖，本發明表面增強拉曼光譜元件的增強效應達107 倍。Figure 7 (a) shows the spectrum of Test Example 2; (b) shows the spectrum of solid pure benzoic acid for a Raman spectroscopy instrument without surface enhancement, comparing (a) the spectrum and (b) the spectrum, The enhancement effect of the invention of the surface-enhanced Raman spectroscopy element is 10 7 times.
測試例3測量不同濃度的苯甲酸水溶液，由圖8顯示濃度與訊號強度的線性關係良好，說明使用本發明表面增強拉曼光譜元件測量濃度為0至1 mM的樣品水溶液，具有良好靈敏度與線性關係。Test Example 3 measures different concentrations of aqueous benzoic acid, and the linear relationship between the concentration and the signal intensity is shown by FIG. 8, indicating that the aqueous solution of the sample having a concentration of 0 to 1 mM is measured using the surface-enhanced Raman spectroscopy element of the present invention, and has good sensitivity and linearity. relationship.
測試例4測量濃度相等體積不同的苯甲酸水溶液，由圖9顯示本發明表面增強拉曼光譜元件測量體積為2至10 μL的水溶性樣品具有良好再現性。Test Example 4 measures an aqueous solution of benzoic acid having a different concentration and a different volume, and it is shown by Fig. 9 that the surface-enhanced Raman spectroscopy element of the present invention has a good reproducibility of a water-soluble sample having a volume of 2 to 10 μL.
圖10顯示測試例5至8之圖譜，相較於使用無表面訊號增強作用之拉曼光譜儀器直接測量之相對應固態化合物的光譜圖，本發明表面增強拉曼光譜元件測量含氮鹼基樣品的增強效應達106 倍。Figure 10 shows the spectra of Test Examples 5 to 8, which are used to measure nitrogen-containing base samples by the surface-enhanced Raman spectroscopy element of the present invention compared to the spectrum of the corresponding solid compound directly measured by a Raman spectroscopy instrument without surface signal enhancement. The enhancement effect is 10 6 times.
測試例9及測試例10分別測量不同濃度的胞嘧啶水溶液及腺嘌呤水溶液，圖11及圖12顯示濃度與訊號強度的線 性關係良好，說明使用本發明表面增強拉曼光譜元件測量濃度為0至100 μM的含氮鹼基樣品，具有良好靈敏度。Test Example 9 and Test Example 10 respectively measured different concentrations of cytosine aqueous solution and adenine aqueous solution, and Figures 11 and 12 show the concentration and signal intensity lines. The good relationship is good, indicating that the nitrogen-containing base sample having a concentration of 0 to 100 μM is measured using the surface-enhanced Raman spectroscopy element of the present invention, and has good sensitivity.
圖13顯示(a)測試例11測得之***酸光譜圖，相較於(b)為無表面增強效果的拉曼光譜儀器測量固態***酸所得之光譜圖，本發明表面增強拉曼光譜元件的增強效應達106 倍。Figure 13 shows (a) the spectrum of the amphetamine measured in Test Example 11, compared to (b) the spectrum obtained by measuring the solid phenylalanine by a Raman spectroscopy apparatus having no surface enhancement effect, the surface-enhanced Raman spectroscopy element of the present invention. The enhancement effect is 10 6 times.
測試例12是測量不同濃度的***酸水溶液。圖14顯示濃度為0至100μM時，濃度與訊號強度的線性關係良好，濃度為200至1000μM時，訊號強度大致相同，說明本發明表面增強拉曼光譜元件可以有效應用至胺基酸定量檢測，且靈敏度優異，偵測極限可達1μM。Test Example 12 is to measure different concentrations of aqueous phenylalanine solution. Figure 14 shows that the linear relationship between the concentration and the signal intensity is good at a concentration of 0 to 100 μM. When the concentration is 200 to 1000 μM, the signal intensity is about the same, indicating that the surface-enhanced Raman spectroscopy element of the present invention can be effectively applied to the quantitative detection of amino acid. Excellent sensitivity and detection limit of 1μM.
圖15顯示(a)測試例13測得之1 mM葡萄糖水溶液光譜圖，相較於(b)無表面增強效果的拉曼光譜儀器測量固態純葡萄糖所得之光譜圖，本發明表面增強拉曼光譜元件的靈敏度較佳，增強效應達106 倍。Figure 15 shows (a) a spectrum of a 1 mM aqueous glucose solution measured in Test Example 13, which is a surface enhanced Raman spectrum of the present invention compared to (b) a spectrogram obtained by measuring a solid pure glucose by a Raman spectroscopy apparatus having no surface enhancement effect. preferably sensitivity of the element, up to 106-fold enhancement effect.
透過測試例14及測試例15可以觀察該柱狀基材之直徑與訊號強度的關係，圖16顯示柱狀基材的直徑為0.3至2.0 mm均可以獲得強度足夠的訊號，具有良好靈敏度。The relationship between the diameter of the columnar substrate and the signal intensity can be observed by Test Example 14 and Test Example 15. FIG. 16 shows that the diameter of the columnar substrate is 0.3 to 2.0 mm, and a sufficient intensity signal can be obtained with good sensitivity.
圖17顯示測試例16至18測量pATP甲醇溶液之光譜圖，可以看出選用PS、PC、PMMA的疏水性高分子膜均可以提供良好的訊號強度，其中測試例18選用PMMA的靈敏度最佳。Figure 17 shows the spectra of the pATP methanol solution measured in Test Examples 16 to 18. It can be seen that the hydrophobic polymer film selected from PS, PC, and PMMA can provide good signal intensity, and the sensitivity of Test Example 18 using PMMA is the best.
圖18顯示測試例19至20測量葡萄糖水溶液之光譜圖，可以看出選用石英及玻璃材質的柱狀基材的均可以得 到良好的訊號強度。Figure 18 shows the spectra of the aqueous solutions of glucose measured in Test Examples 19 to 20. It can be seen that the columnar substrates of quartz and glass can be obtained. To a good signal strength.
圖19為測試例21及測試比較例1及2測量腺嘌呤水溶液之光譜圖。測試比較例1及2是以未設置疏水性高分子膜的平面式表面增強拉曼光譜板進行量測，顯示平面式的表面增強拉曼光譜板，雖具有表面增強效應，但訊號強度小，靈敏度不佳；測試例21選用之表面增強拉曼光譜元件具有柱狀結構且含有該疏水性高分子膜，訊號強度明顯提升，靈敏度佳。由圖20可知，測試例22的訊號強度明顯大於測試比較例3及4，顯示使用柱狀基材及設置該含有疏水性高分子膜，使該表面增強拉曼光譜元件具有明顯提升靈敏度的效果。Fig. 19 is a chart showing the measurement of adenine aqueous solution in Test Example 21 and Test Comparative Examples 1 and 2. Test Comparative Examples 1 and 2 were measured by a planar surface-enhanced Raman spectroscopy plate which was not provided with a hydrophobic polymer film, and showed a planar surface-enhanced Raman spectroscopy plate which had a surface enhancement effect but a small signal intensity. The sensitivity is not good; the surface-enhanced Raman spectroscopy element selected in Test Example 21 has a columnar structure and contains the hydrophobic polymer film, and the signal intensity is remarkably improved, and the sensitivity is good. As can be seen from FIG. 20, the signal intensity of Test Example 22 is significantly larger than that of Test Comparative Examples 3 and 4. It shows that the use of the columnar substrate and the provision of the hydrophobic polymer film make the surface-enhanced Raman spectroscopy element have a significant improvement in sensitivity. .
綜上所述，本發明表面增強拉曼光譜元件結合柱狀基材、疏水性高分子膜及奈米金屬粒子層，透過該基材的柱狀結構，並使該疏水性高分子膜表面粗糙化以吸附更多奈米金屬粒子，使該元件於實際測量時具有較佳的靈敏度及再現性，且特別適用於測量水溶液待測樣品。In summary, the surface-enhanced Raman spectroscopy element of the present invention combines a columnar substrate, a hydrophobic polymer film, and a nano-metal particle layer, penetrates the columnar structure of the substrate, and roughens the surface of the hydrophobic polymer film. The adsorption of more nano metal particles allows the element to have better sensitivity and reproducibility in actual measurement, and is particularly suitable for measuring aqueous samples to be tested.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
1‧‧‧柱狀基材1‧‧‧ columnar substrate
11‧‧‧頂面11‧‧‧ top surface
2‧‧‧疏水性高分子 膜2‧‧‧Hydrophobic polymer membrane
3‧‧‧奈米金屬粒子 層3‧‧‧Nano metal particles Floor
圖1是一示意圖，說明本發明表面增強拉曼光譜元件之第一較佳具體例的結構；圖2是一示意圖，說明本發明表面增強拉曼光譜元件 之第二較佳具體例的結構；圖3是一SEM圖，顯示該奈米金屬粒子層覆蓋於該疏水性高分子膜的情形；圖4是一示意圖，說明本發明表面增強拉曼光譜元件之第三較佳具體例的結構；圖5是一實施例9之含有承載板的表面增強拉曼光譜元件的照片；圖6是一表面增強拉曼光譜的訊號圖，其中(a)測試例1之圖譜，(b)為0.4%(w/v)pATP丙酮溶液之圖譜，(c)為0.4%(w/v)pATP甲醇溶液之圖譜，(d)為固態pATP之圖譜；圖7是一表面增強拉曼光譜的訊號圖，其中(a)測試例2之圖譜，(b)為無表面增強效果的拉曼光譜儀器測量固態純苯甲酸之拉曼圖譜；圖8是一曲線圖，說明測試例3訊號強度與濃度關係；圖9是一關係圖，說明測試例4測量苯甲酸水溶液的訊號強度與體積關係；圖10是一表面增強拉曼光譜的訊號圖，其中(a)為測試例5之圖譜、(b)為測試例6之圖譜、(c)為測試例7之圖譜，及(d)為測試例8之圖譜，以及使用無表面增強效果的拉曼光譜儀器測量之(e)固態腺嘌呤之圖譜、(f)固態胞嘧啶之圖譜、(g)固態胸腺嘧啶之圖譜，及(h)固態尿嘧啶之圖譜；圖11是一關係圖，說明測試例9訊號強度與濃度關 係；圖12是一關係圖，說明測試例10訊號強度與濃度關係；圖13是一表面增強拉曼光譜的訊號圖，其中(a)為測試例11之圖譜，(b)為無表面增強效果的拉曼光譜儀器測量固態純苯甲酸之圖譜；圖14是一曲線圖，說明測試例12訊號強度與濃度關係；圖15是一表面增強拉曼光譜的訊號圖，其中(a)為測試例15之圖譜，(b)為無表面增強效果的拉曼光譜儀器測量純葡萄糖之圖譜；圖16是一曲線圖，其中●表示測試例13，▲表示測試例14，說明訊號強度與柱狀基材直徑的關係；圖17是一表面增強拉曼光譜的訊號圖，說明(a)測試例16、(b)測試例17及(c)測試例18之圖譜；圖18是一表面增強拉曼光譜的訊號圖，說明(a)測試例19及(b)測試例20之圖譜；圖19是一表面增強拉曼光譜的訊號圖，說明(a)測試例21及(b)測試比較例1及(c)測試比較例2之圖譜；及圖20是一表面增強拉曼光譜的訊號圖，說明(a)測試例22及(b)測試比較例3及(c)測試比較例4之圖譜。1 is a schematic view showing the structure of a first preferred embodiment of the surface-enhanced Raman spectroscopy element of the present invention; and FIG. 2 is a schematic view showing the surface-enhanced Raman spectroscopy element of the present invention. The structure of the second preferred embodiment; FIG. 3 is an SEM image showing the case where the nano metal particle layer covers the hydrophobic polymer film; and FIG. 4 is a schematic view showing the surface enhanced Raman spectrum element of the present invention. 3 is a structure of a surface-enhanced Raman spectroscopy element containing a carrier sheet; and FIG. 6 is a signal diagram of a surface-enhanced Raman spectroscopy, wherein (a) a test example 1 map, (b) is a map of 0.4% (w / v) pATP acetone solution, (c) is a map of 0.4% (w / v) pATP methanol solution, (d) is a map of solid pATP; Figure 7 is A signal diagram of surface-enhanced Raman spectroscopy, wherein (a) a map of test example 2, (b) a Raman spectrum of solid-state pure benzoic acid is measured by a Raman spectroscopy instrument without surface enhancement effect; and FIG. 8 is a graph. The relationship between the intensity and concentration of the test sample 3 is illustrated; FIG. 9 is a relationship diagram illustrating the relationship between the signal intensity and the volume of the aqueous solution of benzoic acid in Test Example 4; and FIG. 10 is a signal diagram of a surface enhanced Raman spectrum, wherein (a) is The map of Test Example 5, (b) is the map of Test Example 6, (c) is the map of Test Example 7, and (d) is the test. a map of 8 and (e) a map of solid adenine, (f) a map of solid cytosine, (g) a map of solid thymidine, and (h) solid urine as measured by a Raman spectroscopy instrument without surface enhancement Pyrimidine map; Figure 11 is a relationship diagram showing the intensity and concentration of the test sample 9 Figure 12 is a relationship diagram illustrating the relationship between signal intensity and concentration in Test Example 10; Figure 13 is a signal diagram of a surface-enhanced Raman spectrum, where (a) is the map of Test Example 11, and (b) is no surface enhancement. The effect of the Raman spectroscopy instrument measures the spectrum of solid benzoic acid; Figure 14 is a graph illustrating the relationship between the intensity and concentration of the test sample 12; Figure 15 is a signal diagram of a surface-enhanced Raman spectroscopy, where (a) is the test Figure 15 is a map, (b) is a map of pure glucose measured by a Raman spectroscopy instrument without surface enhancement effect; Figure 16 is a graph, wherein ● indicates test example 13, and ▲ indicates test example 14, indicating signal intensity and columnarity. Figure 17 is a signal diagram of surface-enhanced Raman spectroscopy, illustrating (a) test pattern 16, (b) test case 17 and (c) test case 18; Figure 18 is a surface enhanced pull The signal diagram of the Mann spectrum shows (a) the test pattern 19 and (b) the test pattern 20 map; FIG. 19 is a surface enhanced Raman spectrum signal diagram, illustrating (a) test case 21 and (b) test comparison example 1 and (c) testing the map of Comparative Example 2; and Figure 20 is a signal diagram of a surface enhanced Raman spectrum, Ming (a) and Test Example 22 (b) Example 3 and Comparative Test (c) Test of Comparative Example 4 pattern.
1‧‧‧柱狀基材1‧‧‧ columnar substrate
11‧‧‧頂面11‧‧‧ top surface
2‧‧‧疏水性高分 子膜2‧‧‧Hydraulic high score Submembrane
3‧‧‧奈米金屬粒子層3‧‧‧Nano metal particle layer
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