TWI604187B - Surface-enhanced raman spectroscopy for rapid detection of active ingredients of pesticide products and pesticide residues in agricultural products - Google Patents

Surface-enhanced raman spectroscopy for rapid detection of active ingredients of pesticide products and pesticide residues in agricultural products Download PDF

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TWI604187B
TWI604187B TW105122930A TW105122930A TWI604187B TW I604187 B TWI604187 B TW I604187B TW 105122930 A TW105122930 A TW 105122930A TW 105122930 A TW105122930 A TW 105122930A TW I604187 B TWI604187 B TW I604187B
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organic solvent
pesticide
substrate
sample
raman spectroscopy
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TW201804148A (en
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曾昭銘
游竟維
林韶凱
徐慈鴻
趙偉忠
文昌榮
王永祥
李政謙
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行政院農業委員會農業藥物毒物試驗所
汎鍶科藝股份有限公司
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用以檢驗農藥產品或農作物農藥殘留之表面增強型拉曼光譜檢測方法Surface enhanced Raman spectroscopy method for testing pesticide products or pesticide residues in crops

本發明係關於一種農藥檢驗方法,尤其是一種利用表面增強型拉曼光譜技術(Surface-Enhanced Raman Spectroscopy,SERS)搭配特殊之物質濃縮技術來進行農藥檢驗之拉曼光譜檢測方法。 The invention relates to a pesticide testing method, in particular to a Raman spectroscopy method for detecting pesticides by using Surface-Enhanced Raman Spectroscopy (SERS) combined with special material concentration technology.

台灣的精緻農業對農藥產品使用氾濫,隱藏了許多農藥殘留過高的問題,過去幾年在稻米類、茶葉及各類蔬果皆被檢出超標的農藥殘留,如何建立農作物上的農藥殘留的現場檢測監控機制,已是一項相當重要的課題。 The use of pesticide products in Taiwan's exquisite agriculture has hidden many problems of excessive pesticide residues. In the past few years, pesticide residues have been detected in rice, tea and various fruits and vegetables, and how to establish pesticide residues on crops. Testing and monitoring mechanisms has become a very important issue.

目前能對農藥的成份及濃度做檢測的儀器為液相層析串聯質譜儀(Liquid chromatography tandem mass spectrometer,LC/MS-MS)或氣相層析串聯質譜儀(Gas chromatography tandem mass spectrometer,GC/MS-MS),其具有檢測靈敏度高之優點,但其缺點是僅能在實驗室進行,且耗費時間較長,尤其是儀器在進行檢測前還需先利用QuEChERS方法(Quick,Easy,Cheap,Effective,Rugged,Safe)對樣品進行萃取及淨化處理,此QuEChERS方法大約需花費2 個小時,才能從樣品中取得所需要的樣品檢液,因此很難在第一時間做監控,阻絕農藥殘留的問題。 The current instrument for detecting the composition and concentration of pesticides is liquid chromatography tandem mass spectrometer (LC/MS-MS) or gas chromatography tandem mass spectrometer (GC/). MS-MS), which has the advantage of high detection sensitivity, but its disadvantage is that it can only be carried out in the laboratory, and it takes a long time, especially the instrument needs to use the QuEChERS method before the test (Quick, Easy, Cheap, Effective, Rugged, Safe) extracts and purifies the sample. This QuEChERS method costs approximately 2 In an hour, the required sample liquid can be taken from the sample, so it is difficult to monitor the first time and block the problem of pesticide residues.

有別於實驗室之質譜儀檢測,台灣專利第M506286號揭露另一種成品農藥檢測裝置,其係利用SERS基板搭配拉曼光譜儀達到快速檢出成品農藥的有效成分之目的。一般而言,拉曼光譜技術之成敗最關鍵因素是拉曼訊號之強度。為增強拉曼訊號,該專利在取得拉曼訊號前,待測樣品會先經歷一雷射前置照射程序,也就是增加雷射光照射時間約2-3秒,以增進農藥分子與SERS基板上的金屬結構之吸附程度,藉此提高拉曼訊號之強度。 Different from the mass spectrometer test in the laboratory, Taiwan Patent No. M506286 discloses another finished pesticide detection device, which uses the SERS substrate with Raman spectrometer to achieve the purpose of quickly detecting the active ingredients of the finished pesticide. In general, the most critical factor in the success or failure of Raman spectroscopy is the intensity of the Raman signal. In order to enhance the Raman signal, before the Raman signal is obtained, the sample to be tested will first undergo a laser pre-irradiation procedure, that is, the laser irradiation time is increased by about 2-3 seconds to enhance the pesticide molecules and the SERS substrate. The degree of adsorption of the metal structure, thereby increasing the intensity of the Raman signal.

另一方面,在中國申請之CN104749159及CN104931483等專利案亦揭露類似之拉曼光譜檢測方法,以應用在農藥殘留之檢驗。其中,為增強拉曼訊號之強度,該些專利係先將該待測樣品之處理液與金屬奈米材料增強劑(例如:銀或金奈米材料)混合而製成,再進行雷射光照射,以得到足夠的拉曼光譜。 On the other hand, patents such as CN104749159 and CN104931483, which are applied in China, also disclose similar Raman spectroscopy methods for the application of pesticide residues. In order to enhance the intensity of the Raman signal, the patents are prepared by mixing the treatment liquid of the sample to be tested with a metal nanomaterial material enhancer (for example, silver or gold nanomaterial), and then irradiating the laser light. To get enough Raman spectra.

有別於先前技術,本發明提供另一種能於農藥或化學物質檢測時增強拉曼訊號的方法,其主要是結合傳統之表面增強型拉曼光譜檢測技術以及獨創之濃縮技術來對農藥有效成份及農作物農藥殘留進行快速的檢測,藉由此特殊之濃縮技術能有效地提升拉曼訊號之強度,大大提高檢測靈敏度及可靠度。 Different from the prior art, the present invention provides another method for enhancing the Raman signal when detecting pesticides or chemicals, mainly combining traditional surface enhanced Raman spectroscopy and original concentration technology to the active ingredients of pesticides. And the rapid detection of pesticide residues in crops, by which special concentration technology can effectively enhance the intensity of Raman signals, greatly improving detection sensitivity and reliability.

具體而言,本發明之表面增強型拉曼光譜檢測方法,包括底下步驟:(a).對一待測樣品進行萃取及淨化,形成一樣品檢液;(b).將萃取淨化後之樣品檢液滴附在一SERS基板,以使該樣品檢液之化學分子吸附於該SERS基板上;(c).續以高揮發性之有機溶劑滴附於前述吸附有化學分子之SERS基板上,以使化學分子復溶於該有機溶劑中,進而浮出該SERS基板表面;(d).以光照射該SERS基板,以使該SERS基板上之有機溶劑受熱揮發,而留下之化學分子 則逐漸集中至一濃縮區域;(e).再以較高能量之雷射光照射該濃縮區域,以使該濃縮區域中之化學分子較深層地吸附於該SERS基板,與其中的奈米金屬材料緊密結合,藉以形成固相的一光譜量測區;及(f).以雷射光聚焦於該光譜量測區,進行拉曼光譜量測。 Specifically, the surface enhanced Raman spectroscopy method of the present invention comprises the following steps: (a) extracting and purifying a sample to be tested to form a sample test solution; (b) extracting the sample after purification Detecting droplets attached to a SERS substrate to adsorb chemical molecules of the sample liquid on the SERS substrate; (c) continuing to deposit a highly volatile organic solvent on the SERS substrate having the chemical molecules adsorbed thereon, So that the chemical molecules are redissolved in the organic solvent to float the surface of the SERS substrate; (d) irradiating the SERS substrate with light to cause the organic solvent on the SERS substrate to be volatilized by heat, leaving chemical molecules behind Gradually concentrating to a concentrated region; (e) illuminating the concentrated region with higher energy laser light so that chemical molecules in the concentrated region are more deeply adsorbed on the SERS substrate, and the nano metal material therein Tightly combined to form a spectral measurement region of the solid phase; and (f) focusing on the spectral measurement region with laser light for Raman spectroscopy.

較佳地,步驟(a)中進行萃取所使用之萃取溶劑係選自丙酮、甲醇、乙腈及含醋酸之乙腈溶液所組成之群組。 Preferably, the extraction solvent used for the extraction in the step (a) is selected from the group consisting of acetone, methanol, acetonitrile and an acetic acid-containing acetonitrile solution.

較佳地,步驟(a)中所進行之淨化係使萃取後之待測液依序通過一淨化管柱以及一微米孔徑之濾膜。 Preferably, the purification performed in the step (a) is such that the extracted liquid to be tested sequentially passes through a purification column and a filter membrane of one micron pore size.

較佳地,步驟(c)中所使用之該高揮發性的有機溶劑係由丙酮、甲醇及乙醇中之至少一者稀釋而成。 Preferably, the highly volatile organic solvent used in the step (c) is diluted with at least one of acetone, methanol and ethanol.

較佳地,該高揮發性之有機溶劑係以去離子水、乙腈及甲醇中之任一者稀釋。 Preferably, the highly volatile organic solvent is diluted with any of deionized water, acetonitrile and methanol.

較佳地,步驟(d)中所使用的光係紅外線,其波長介於760nm~2000nm,且其光源之輸出功率大於1mW;而步驟(e)中所使用的紅外線之波長介於760nm~1500nm,且其光源之輸出功率不大於500mW。 Preferably, the light-based infrared light used in the step (d) has a wavelength between 760 nm and 2000 nm, and the output power of the light source is greater than 1 mW; and the wavelength of the infrared light used in the step (e) is between 760 nm and 1500 nm. And the output power of the light source is not more than 500mW.

較佳地,步驟(e)中所使用之雷射光係選用單一波長的雷射光。 Preferably, the laser light used in step (e) is a single wavelength of laser light.

從另一角度觀之,本發明係提供一種化學物質濃縮方法,其包括底下步驟:(a).將一樣品檢液滴附在一金屬基板(例如SERS基板或其他純金屬的基板),以使該樣品檢液之化學分子吸附於該金屬基板上;(b).續以高揮發性之有機溶劑(例如以去離子水稀釋的丙酮容液)滴附於前述吸附有化學分子之金屬基板上,以使化學分子復溶於該有機溶劑中,進而浮出該金屬基板表面;及(c).使該金屬基板上之有機溶劑受熱揮發,留下之化學分子逐漸集中至一濃縮區域。 Viewed from another angle, the present invention provides a chemical concentration method comprising the following steps: (a) attaching a sample to a metal substrate (such as a SERS substrate or other pure metal substrate) to The chemical molecules of the sample liquid are adsorbed on the metal substrate; (b) continuing to adhere to the metal substrate adsorbed with the chemical molecules by a highly volatile organic solvent (for example, an acetone solution diluted with deionized water) The chemical molecules are redissolved in the organic solvent to float the surface of the metal substrate; and (c) the organic solvent on the metal substrate is volatilized by heat, and the remaining chemical molecules are gradually concentrated to a concentrated region.

較佳地,步驟(c)係以較低能量之紅外線照射於該金屬基板上,以使該金屬基板上之有機溶劑快速揮發。 Preferably, step (c) is irradiated onto the metal substrate with lower energy infrared rays to rapidly evaporate the organic solvent on the metal substrate.

較佳地,該化學物質濃縮方法更包括在步驟(c)之後, 續以較高能量之紅外線雷射光照射該濃縮區域,使化學分子更加緊密地吸附於該金屬基板上。 Preferably, the chemical concentration method further comprises after step (c), The concentrated region is irradiated with higher energy infrared laser light to more closely adsorb the chemical molecules on the metal substrate.

此化學物質濃縮方法除了可應用在拉曼光譜檢測,但不限於此,亦可以應用在其他的領域。 This chemical concentration method can be applied to Raman spectroscopy, but is not limited thereto, and can be applied to other fields.

1‧‧‧表面增強型拉曼散射基板 1‧‧‧ Surface-enhanced Raman scattering substrate

11‧‧‧矽基板 11‧‧‧矽 substrate

12‧‧‧金屬奈米或微米結構 12‧‧‧Metal nano or micro structure

2‧‧‧雷射光源 2‧‧‧Laser light source

3‧‧‧拉曼光譜儀 3‧‧‧Raman Spectrometer

4‧‧‧樣品檢液 4‧‧‧ Sample test solution

41‧‧‧化學分子(農藥分子) 41‧‧‧Chemical molecules (pesticide molecules)

5‧‧‧有機溶劑 5‧‧‧Organic solvents

L1‧‧‧紅外線 L1‧‧‧Infrared

L2‧‧‧紅外線 L2‧‧‧Infrared

第一圖係本發明之拉曼光譜檢測系統的簡易示意圖。 The first figure is a simplified schematic of the Raman spectroscopy detection system of the present invention.

第二圖係本發明之拉曼光譜檢測方法的流程示意圖。 The second figure is a schematic flow chart of the Raman spectroscopy detection method of the present invention.

第三至十圖係顯示本發明以SERS基板1為載具進行化學物質濃縮的過程。 The third to tenth drawings show the process of concentrating a chemical substance by the present invention using the SERS substrate 1 as a carrier.

第十一圖係利用本發明方法檢測成品農藥芬殺松(Fenthion)的拉曼檢測光譜圖。 The eleventh figure is a Raman detection spectrum of the finished pesticide Fenthion using the method of the present invention.

第十二圖係利用本發明方法檢測成品農藥加保利(Carbaryl)的拉曼檢測光譜圖。 The twelfth figure is a Raman detection spectrum of the finished pesticide plus Carbaryl using the method of the present invention.

第十三圖係利用傳統方法檢測成品農藥三落松(Triazophos)的拉曼檢測光譜圖,其中滴附於SERS基板之分子並未經過如第五至十圖所示之復溶濃縮過程。 The thirteenth image is a conventional method for detecting the Raman detection spectrum of the finished pesticide Triazophos, in which the molecules dropped on the SERS substrate are not subjected to the reconstitution concentration process as shown in Figures 5 to 10.

第十四圖係利用本發明方法檢測成品農藥三落松(Triazophos)的拉曼檢測光譜圖,其中滴附於SERS基板之分子有經過復溶濃縮過程。 The fourteenth figure is a Raman detection spectrum of the finished pesticide Triazophos by the method of the present invention, wherein the molecules dropped on the SERS substrate are subjected to a reconstitution and concentration process.

第十五圖係利用本發明方法檢測溼稻穀中殘留有農藥三落松(Triazophos)及農藥芬殺松(Fenthion)的拉曼檢測光譜圖。 The fifteenth figure uses the method of the present invention to detect the Raman detection spectrum of the residual triazophos and the pesticide Fenthion in the wet rice.

第一及二圖顯示本發明之農藥檢測系統及方法的一個較佳實施例,其中該農藥檢測方法主要是以一表面增強型拉曼散射基板1(Surface-Enhanced Raman Scattering Substrate,下稱:SERS 基板)作為檢測載具,並搭配一雷射光源2及一拉曼光譜儀3(Raman spectrometer)來達成現場及時農藥檢測,又可稱為表面增強型拉曼光譜檢測方法。其中,該SERS基板1包括一面積為2.2mm x 2.2mm的矽基板11及利用物理氣相沉積技術成長在之該矽基板11上的一金屬奈米或微米結構12,其中金屬可選自金、銀、銅等材料,例如厚度為320nm之銀奈米柱結構(silver nanopillars)。 The first and second figures show a preferred embodiment of the pesticide detection system and method of the present invention, wherein the pesticide detection method is mainly a Surface-Enhanced Raman Scattering Substrate (SERS). The substrate is used as a detection vehicle, and is combined with a laser light source 2 and a Raman spectrometer to achieve on-site pesticide detection. It can also be called surface enhanced Raman spectroscopy. The SERS substrate 1 includes a germanium substrate 11 having an area of 2.2 mm x 2.2 mm and a metal nano or micro structure 12 grown on the germanium substrate 11 by physical vapor deposition techniques, wherein the metal may be selected from gold. Materials such as silver and copper, such as silver nanopillars having a thickness of 320 nm.

參閱第二圖,本發明之表面增強型拉曼光譜檢測方法大致可分為前處理、濃縮及量測等三大階段。其中,前處理階段可利用本發明所述之簡便的萃取淨化(步驟201)方法即可,或是採用較為費時的傳統QuEChERS方法。濃縮階段主要係如第二圖虛線框內所包含之靜置乾燥(步驟202)、分子復溶(步驟203)、溶劑揮發(步驟204)及附著結合(步驟205)等四個步驟;而量測階段主要是進行拉曼散射光譜之量測(步驟206),詳如下述:具體而言,本發明之表面增強型拉曼光譜檢測方法包括底下步驟:首先,對一待測樣品(例如農藥產品或農作物)進行萃取及淨化(步驟201),形成一樣品檢液。在此步驟中,可將樣品粉碎或直接取適當樣品數量,再加入萃取溶劑以振盪或搖晃方式混合。其中,該萃取溶劑可選自丙酮、甲醇、乙腈及含醋酸之乙腈溶液等有機溶劑。接著,取20mL~0.2mL的萃取液,並使其依序通過一淨化管柱以及一微米孔徑之濾膜,以進行淨化得到一樣品檢液,以完成前處理階段。 Referring to the second figure, the surface enhanced Raman spectroscopy method of the present invention can be roughly divided into three stages: pretreatment, concentration and measurement. Wherein, the pre-treatment stage can be carried out by the simple extraction and purification (step 201) method described in the present invention, or by the relatively time-consuming conventional QuEChERS method. The concentration stage is mainly composed of four steps of static drying (step 202), molecular reconstitution (step 203), solvent evaporation (step 204), and adhesion bonding (step 205) included in the dotted line frame of the second figure; The measurement phase is mainly performed by measuring the Raman scattering spectrum (step 206), as described in detail below. Specifically, the surface enhanced Raman spectroscopy method of the present invention comprises the following steps: First, a sample to be tested (for example, a pesticide) The product or crop) is subjected to extraction and purification (step 201) to form a sample test solution. In this step, the sample may be pulverized or directly taken to the appropriate sample amount, and then added to the extraction solvent to be mixed by shaking or shaking. The extraction solvent may be selected from the group consisting of acetone, methanol, acetonitrile, and an organic solvent such as an acetic acid-containing acetonitrile solution. Next, 20 mL to 0.2 mL of the extract is taken and passed through a purification column and a micron-diameter filter membrane for purification to obtain a sample test liquid to complete the pretreatment stage.

接著,如第三圖所示,將取10μL~0.2μL萃取淨化後之樣品檢液4滴附在一SERS基板1。待靜置乾燥(步驟202)後,該樣品檢液4之化學分子41將分散並吸附於該SERS基板1上,與該金屬奈米或微米結構12結合,如第四圖所示。 Next, as shown in the third figure, 10 μL to 0.2 μL of the sample liquid 4 after extraction and purification is attached to a SERS substrate 1. After standing to dry (step 202), the chemical molecules 41 of the sample test solution 4 will be dispersed and adsorbed on the SERS substrate 1 in combination with the metal nano or microstructure 12, as shown in the fourth figure.

如第五圖所示,續以高揮發性之有機溶劑5滴附於前述吸附有化學分子41之SERS基板1上,以使化學分子41復溶於該有機溶劑5中(步驟203),進而浮出該SERS基板1的表面,如第六圖所示。其中,該高揮發性之有機溶劑係由丙酮、甲醇及乙醇 中之至少一者稀釋而成,且稀釋劑可選用去離子水、乙腈及甲醇中之任一者稀釋。 As shown in the fifth figure, a highly volatile organic solvent 5 is continuously applied to the SERS substrate 1 on which the chemical molecules 41 are adsorbed, so that the chemical molecules 41 are re-dissolved in the organic solvent 5 (step 203). The surface of the SERS substrate 1 is floated as shown in the sixth figure. Among them, the highly volatile organic solvent is made up of acetone, methanol and ethanol. At least one of them is diluted, and the diluent may be diluted with any one of deionized water, acetonitrile and methanol.

緊接著,如第七圖所示,先以光束大但能量較低之紅外線L1照射於該SERS基板1上,以使該SERS基板1上之有機溶劑5受熱揮發(步驟204),如第八圖所示,而留下之化學分子41則逐漸集中至一濃縮區域(未標號),如第九圖所示。其中,該紅外線L1之波長可介於760nm~2000nm,可選用多波長的紅外線,且其光源之輸出功率大於1mW,目的在使有機溶劑快速揮發。 Then, as shown in the seventh figure, the infrared light L1 having a large light beam but low energy is first irradiated onto the SERS substrate 1 to cause the organic solvent 5 on the SERS substrate 1 to be volatilized by heat (step 204), such as the eighth. As shown in the figure, the remaining chemical molecules 41 are gradually concentrated to a concentrated area (not labeled) as shown in the ninth figure. Wherein, the wavelength of the infrared light L1 can be between 760 nm and 2000 nm, and multiple wavelengths of infrared light can be selected, and the output power of the light source is greater than 1 mW, so as to rapidly evaporate the organic solvent.

隨後,參閱第九及十圖,再以光束小但能量較高之紅外線L2照射該濃縮區域,以使該濃縮區域中之化學分子41較深層地吸附於該SERS基板1,與其中的奈米金屬材料緊密結合(步驟205),以形成固相的一光譜量測區(未標號),完成濃縮階段。其中,紅外線L2之波長可介於760nm~1500nm,較佳係選用單一波長的紅外線雷射光,且其光源之輸出功率不大於500mW,目的在加強化學分子與奈米金屬材料之結合強度。 Subsequently, referring to the ninth and tenth views, the concentrated region is irradiated with the infrared light L2 having a small beam but a higher energy, so that the chemical molecules 41 in the concentrated region are adsorbed deeper on the SERS substrate 1 with the nanometer therein. The metal material is tightly bonded (step 205) to form a spectral measurement zone (not labeled) of the solid phase to complete the concentration phase. The wavelength of the infrared light L2 may be between 760 nm and 1500 nm, preferably using a single wavelength of infrared laser light, and the output power of the light source is not more than 500 mW, in order to strengthen the bonding strength between the chemical molecule and the nano metal material.

復參閱第一圖,待濃縮階段完成後,便可進入量測階段,也就是以該雷射光源2之雷射光聚焦於該光譜量測區,著手進行拉曼光譜量測。當濃縮且吸附於SERS基板之奈米銀粒子的化學分子(農藥分子)被雷射聚焦而激發出拉曼光譜,藉由官能基結構差異所表現的拉曼光譜特徵不同,據以判斷化學分子結構。其中,該雷射光之波長可選自1064nm,785nm、633nm、532nm或514nm等可見光或近紅外光之範圍,而拉曼光譜之拉曼位移(Raman Shift)量測範圍則介於200cm-1至4000cm-1。 Referring to the first figure, after the concentration phase is completed, the measurement phase can be entered, that is, the laser light of the laser source 2 is focused on the spectral measurement area, and the Raman spectrum measurement is started. When the chemical molecules (pesticide molecules) concentrated and adsorbed on the SERS substrate are laser-focused to excite the Raman spectrum, the Raman spectra are different by the difference in functional structure, and the chemical molecules are judged accordingly. structure. Wherein, the wavelength of the laser light may be selected from the range of visible light or near-infrared light such as 1064 nm, 785 nm, 633 nm, 532 nm or 514 nm, and the Raman Shift measurement range of the Raman spectrum is between 200 cm-1 and 4000cm-1.

綜上所述,當該樣品檢液4滴附於SERS基板1後,檢液中的待測物分子(也就是農藥分子)將會與檢液中的其他非待測物分子競爭吸附於SERS基板1表面,待靜置乾燥(步驟202)後,該些分子會廣泛分布並吸附於SERS基板1。隨後再以特定溶劑配比混合之溶液將吸附的待測物分子復溶(步驟203),並以適當功率之光照進行濃縮(步驟204-205),藉由此一化學物質濃縮方法,可有 效集中農藥分子,增強拉曼光譜訊號。值得注意的是,復溶時使用之該溶液(也就是高揮發有機溶劑)須兼具可揮發及將待測物分子復溶之特性,並保護待測物分子免於在光照濃縮過程被功率過強的雷射光破壞而降解分子結構,造成訊號強度降低或誤判。 In summary, when the sample liquid 4 is attached to the SERS substrate 1, the molecules of the test object (that is, the pesticide molecules) in the test liquid will compete with other non-substance molecules in the test liquid for adsorption to the SERS. After the surface of the substrate 1 is left to dry (step 202), the molecules are widely distributed and adsorbed on the SERS substrate 1. Then, the adsorbed analyte molecules are reconstituted by a solution mixed with a specific solvent ratio (step 203), and concentrated by light of appropriate power (steps 204-205), whereby a chemical concentration method may have Concentrate on pesticide molecules and enhance Raman spectroscopy signals. It is worth noting that the solution used in reconstitution (that is, the highly volatile organic solvent) must have the characteristics of being volatile and re-dissolving the molecules of the analyte, and protecting the molecules of the analyte from being absorbed in the light concentration process. Excessive laser light destroys the molecular structure, causing the signal strength to decrease or misjudge.

藉由上述方法,農作物樣品經由簡易萃取及快速淨化濃縮步驟後,滴附於SERS基板進行拉曼光譜檢測,可在現場十分鐘之內完成,並由電腦判讀得知殘留的化學物質種類及含量,可大大增進農藥檢測效率,在第一時間阻絕不合格之農藥品。 By the above method, the crop sample is attached to the SERS substrate for Raman spectroscopy after simple extraction and rapid purification and concentration steps, and can be completed within ten minutes on the spot, and the type and content of residual chemical substances are read by the computer. It can greatly improve the efficiency of pesticide testing and block unqualified pesticides in the first time.

底下將列舉幾項實例詳細說明: A few examples will be detailed below:

實驗一:成品農藥芬殺松(Fenthion)之檢測 Experiment 1: Detection of the finished pesticide Fenthion

請參閱第十一圖成品農藥芬殺松之拉曼檢測光譜圖,其中測試樣品為50%濃度、廠牌利霸山之芬殺松乳劑(有機磷類)。首先,將該測試樣品利用丙酮將濃度稀釋至100ppm,迴旋振盪30秒後,取0.5ml混合液通過一淨化管柱,該淨化管柱含適量之C18及PSA粉末,且該淨化管柱串接一0.2μm孔徑之Nylon過濾片,以進行過濾。隨後再利用微量滴管取2μl淨化後之樣品檢液滴在SERS基板上,等待乾燥。其中,該SERS基板具有面積為2.2mm x 2.2mm之矽基板以及沉積在該矽基板上厚度320nm的銀奈米柱結構。乾燥後之農藥分子將吸附在銀奈米柱結構上,再以2μl的丙酮:去離子水(1:1,v/v)混合液(也就是高揮發有機溶劑)滴附於SERS基板使農藥分子復溶。隨後先以波長808nm、功率200mW~300mW的紅外線雷射光照射該SERS基板,使有機溶劑快速揮發,留下濃縮的農藥分子。接著,再以波長785nm、功率100mW的紅外線雷射光照射該SERS基板,使濃縮的農藥分子進一步吸附在銀奈米柱結構上,完成檢品的製備。最後在拉曼光譜量測時,雷射光源係採用785nm之波長、使用功率為80mW、透鏡倍率4X、積分時間為500ms、平均次數為32次。由量測結果得知,芬殺松農藥分子之拉曼檢測光譜主要特徵峰值位於1044cm-1、1224cm-1、1569cm-1等處,與標準樣品的光譜一致。值得注意的是,拉曼檢測光譜中之520 cm-1處為SERS基板下層之矽基板本身之拉曼訊號,並非農藥分子使然。此檢測方式整體檢測時間少於10分鐘,可立即定性判斷成品農藥之有效成份種類。 Please refer to the eleventh figure of the finished pesticide Fenicide pine Raman detection spectrum, in which the test sample is 50% concentration, the brand Libashan Fenicide Loose Emulsion (organophosphorus). First, the test sample is diluted to 100 ppm by acetone, and after swirling for 30 seconds, 0.5 ml of the mixed solution is passed through a purification column containing an appropriate amount of C18 and PSA powder, and the purification column is connected in series. A 0.2 μm pore size Nylon filter was used for filtration. Subsequently, 2 μl of the purified sample was spotted on a SERS substrate using a micropipette and waited for drying. Wherein, the SERS substrate has a germanium substrate having an area of 2.2 mm x 2.2 mm and a silver nano column structure having a thickness of 320 nm deposited on the germanium substrate. The dried pesticide molecules will be adsorbed on the silver nano column structure, and then 2μl of acetone: deionized water (1:1, v/v) mixture (that is, high volatile organic solvent) is added to the SERS substrate to make the pesticide. Molecular reconstitution. Subsequently, the SERS substrate is irradiated with infrared laser light having a wavelength of 808 nm and a power of 200 mW to 300 mW to rapidly evaporate the organic solvent, leaving a concentrated pesticide molecule. Next, the SERS substrate is irradiated with infrared laser light having a wavelength of 785 nm and a power of 100 mW, and the concentrated pesticide molecules are further adsorbed on the silver nano column structure to complete the preparation of the sample. Finally, in the Raman spectroscopy measurement, the laser source uses a wavelength of 785 nm, a power of 80 mW, a lens magnification of 4X, an integration time of 500 ms, and an average number of times of 32 times. According to the measurement results, the main characteristic peaks of the Raman detection spectrum of the pesticides of Fenicides were located at 1044 cm-1, 1224 cm-1, 1569 cm-1, etc., which were consistent with the spectra of the standard samples. It is worth noting that 520 in the Raman detection spectrum The cm-1 is the Raman signal of the substrate itself under the SERS substrate, which is not caused by pesticide molecules. The overall detection time of this test method is less than 10 minutes, and the effective component of the finished pesticide can be determined qualitatively immediately.

實驗二:成品農藥加保利之檢測 Experiment 2: Detection of finished pesticides plus Poly

請參閱第十二圖成品農藥加保利(Carbaryl)之拉曼檢測光譜圖,其中測試樣品為85%濃度、可溼性粉劑型的加保利農藥(胺基甲酸鹽類)。首先,將該測試樣品利用丙酮將濃度稀釋至100ppm,迴旋振盪30秒後,取0.5ml混合液通過一淨化管柱,該淨化管柱含適量之C18及PSA粉末,且該淨化管柱串接一0.2μm孔徑之Nylon過濾片,以進行過濾。隨後再利用微量滴管取2μl淨化後之樣品檢液滴在SERS基板上,等待乾燥。其中,該SERS基板具有面積為2.2mm x 2.2mm之矽基板以及沉積在該矽基板上之厚度320nm的銀奈米柱結構。乾燥後農藥分子吸附在該銀奈米柱結構上,再以2μl的甲醇:去離子水(1:1,v/v)混合液(也就是高揮發有機溶劑)滴附於SERS基板使農藥分子復溶。隨後先以波長808nm、功率200mW~300mW的紅外線雷射光照射該SERS基板,使有機溶劑快速揮發,留下濃縮的農藥分子。接著,再以波長785nm、功率100mW的紅外線雷射光照射該SERS基板,使濃縮的農藥分子進一步吸附在銀奈米柱結構上,完成檢品的製備。而在進行拉曼光譜量測時,雷射光源係採用785nm之雷射波長、使用功率為100mW、透鏡倍率4X、積分時間為500ms、平均次數為32次。由量測結果得知,加保利農藥分子之拉曼檢測光譜主要特徵峰值位於1385cm-1及1420cm-1等處,與標準樣品光譜一致。同樣地,拉曼檢測光譜中之520cm-1處為SERS基板下層之矽基板本身之拉曼訊號,並非農藥分子使然。 Please refer to Figure 12 for the Raman detection spectrum of the finished pesticide plus Carbaryl. The test sample is an 85% strength, wettable powder type of Poly-Pesticide (Aminoformate). First, the test sample is diluted to 100 ppm by acetone, and after swirling for 30 seconds, 0.5 ml of the mixed solution is passed through a purification column containing an appropriate amount of C18 and PSA powder, and the purification column is connected in series. A 0.2 μm pore size Nylon filter was used for filtration. Subsequently, 2 μl of the purified sample was spotted on a SERS substrate using a micropipette and waited for drying. Wherein, the SERS substrate has a germanium substrate having an area of 2.2 mm x 2.2 mm and a silver nano column structure having a thickness of 320 nm deposited on the germanium substrate. After drying, the pesticide molecules are adsorbed on the silver nano column structure, and the mixture of 2 μl of methanol: deionized water (1:1, v/v) (that is, a highly volatile organic solvent) is attached to the SERS substrate to make the pesticide molecule. Reconstituted. Subsequently, the SERS substrate is irradiated with infrared laser light having a wavelength of 808 nm and a power of 200 mW to 300 mW to rapidly evaporate the organic solvent, leaving a concentrated pesticide molecule. Next, the SERS substrate is irradiated with infrared laser light having a wavelength of 785 nm and a power of 100 mW, and the concentrated pesticide molecules are further adsorbed on the silver nano column structure to complete the preparation of the sample. In the Raman spectroscopy measurement, the laser source uses a laser wavelength of 785 nm, a power of 100 mW, a lens magnification of 4X, an integration time of 500 ms, and an average number of times of 32 times. According to the measurement results, the main characteristic peaks of the Raman detection spectrum of the poly-protective pesticide molecules are located at 1385 cm-1 and 1420 cm-1, which are consistent with the standard sample spectrum. Similarly, the Raman signal at 520 cm-1 in the Raman detection spectrum is the substrate itself in the lower layer of the SERS substrate, not the pesticide molecule.

實驗三:成品農藥三落松有/無濃縮之檢測比較 Experiment 3: Comparison of the detection of the finished pesticides

請參閱第十三圖成品農藥三落松(Triazophos)之拉曼檢測光譜圖,其中係將農藥成品利用丙酮將濃度稀釋至10ppm,迴旋振盪30秒後,取0.5ml混合液通過一淨化管柱,該淨化管柱含適量之C18及PSA粉末,且該淨化管柱串接一0.2μm孔徑之Nylon 過濾片,以進行過濾。隨後再利用微量滴管取2μl淨化後之樣品檢液滴在SERS基板上,該SERS基板具有面積為2.2mm x 2.2mm之矽基板以及沉積在該矽基板上之厚度320nm的銀奈米柱結構。乾燥後農藥分子吸附將在該銀奈米柱結構上。此時,若乾燥後直接以拉曼光譜儀量測即可得到如第十三圖所示之拉曼光譜圖。反之,若乾燥後使農藥分子繼續完成復溶濃縮程序再進行拉曼光譜量測,即可得到如第十四圖所示之拉曼光譜圖。換言之,前者的實驗中,樣品檢液沒有進行復溶濃縮程序,可作為後者有進行復溶濃縮程序者之參照。 Please refer to the Raman detection spectrum of the finished pesticide Triazophos in the thirteenth figure, in which the pesticide product is diluted to 10 ppm by acetone, and after swirling for 30 seconds, 0.5 ml of the mixture is passed through a purification column. The purification column contains an appropriate amount of C18 and PSA powder, and the purification column is connected in series with a 0.2 μm aperture Nylon Filter the filter for filtration. Subsequently, 2 μl of the purified sample was spotted on a SERS substrate by using a micropipette having a ruthenium substrate having an area of 2.2 mm x 2.2 mm and a silver nanocolumn structure having a thickness of 320 nm deposited on the ruthenium substrate. . After drying, the pesticide molecules will adsorb on the silver nanocolumn structure. At this time, if it is directly measured by a Raman spectrometer after drying, a Raman spectrum as shown in Fig. 13 can be obtained. On the other hand, if the pesticide molecules continue to complete the reconstitution concentration procedure after drying and then perform Raman spectroscopy, a Raman spectrum as shown in Fig. 14 can be obtained. In other words, in the former experiment, the sample test solution was not subjected to a reconstitution and concentration process, and it can be used as a reference for those who have undergone reconstitution and concentration procedures.

詳而言之,若乾燥後續以2μl的甲醇:去離子水(1:1,v/v)混合液(也就是高揮發有機溶劑)滴附於SERS基板使農藥分子復溶,隨後再進行照光濃縮。其中,在濃縮過程中係以波長808nm、功率200mW~300mW的紅外線雷射光照射該SERS基板,使有機溶劑快速揮發,留下濃縮的農藥分子。接著,再以波長785nm、功率100mW的紅外線雷射光照射該SERS基板,使濃縮的農藥分子進一步吸附在銀奈米柱結構上,完成檢品的製備。最後再置入拉曼光譜儀進行SERS光譜量測,得到如第十四圖之拉曼光譜圖,其中,拉曼光譜量測之雷射光源係採用785nm之波長、使用功率為80mW、透鏡倍率4X、積分時間為500ms、平均次數為32次。由量測結果得知,三落松農藥分子之拉曼光譜主要特徵峰值位於983cm-1、1004cm-1、1410cm-1、1548cm-1、及1599cm-1處等,與標準樣品光譜一致。更重要的是,第十四圖之拉曼光譜圖的訊號強度較第十三圖增強將近5倍,由此可見本發明的復溶濃縮方法確實能增強拉曼訊號,大大提升檢測靈敏度。 In detail, if it is dried, 2μl of methanol: deionized water (1:1, v/v) mixture (that is, high volatile organic solvent) is added to the SERS substrate to reconstitute the pesticide molecules, and then illuminate. concentrate. Among them, in the concentration process, the SERS substrate is irradiated with infrared laser light having a wavelength of 808 nm and a power of 200 mW to 300 mW, so that the organic solvent is quickly volatilized, leaving concentrated pesticide molecules. Next, the SERS substrate is irradiated with infrared laser light having a wavelength of 785 nm and a power of 100 mW, and the concentrated pesticide molecules are further adsorbed on the silver nano column structure to complete the preparation of the sample. Finally, a Raman spectrometer was placed for SERS spectroscopy to obtain a Raman spectrum as shown in Fig. 14. The laser source of Raman spectroscopy was 785 nm, the power was 80 mW, and the lens magnification was 4X. The integration time is 500ms and the average number of times is 32. According to the measurement results, the main characteristic peaks of the Raman spectra of the three falling pine pesticide molecules are located at 983 cm-1, 1004 cm-1, 1410 cm-1, 1548 cm-1, and 1599 cm-1, which are consistent with the standard sample spectrum. More importantly, the signal intensity of the Raman spectrum of the fourteenth figure is nearly five times stronger than that of the thirteenth figure. It can be seen that the reconstitution and concentration method of the present invention can enhance the Raman signal and greatly improve the detection sensitivity.

實驗四:農作物之多種農藥殘留檢測 Experiment 4: Detection of multiple pesticide residues in crops

第十五圖係溼稻穀殘留有三落松(Triazophos)及芬殺松(Fenthion)等農藥之拉曼檢測光譜圖。一般而言,稻穀在烘乾及去殼後,在成為糙米及白米時之農藥殘留濃度將遠少於5ppm,故而在本實驗中,測試樣品是在溼稻穀中添加有5ppm的三落松 (Triazophos)及5ppm的芬殺松(Fenthion)。首先,將上述10克測試樣品與10ml丙酮混合後,手搖30秒並取出1ml萃取溶液通過一淨化管柱,該淨化管柱內需同時加入PSA、C18、MgSO4及GCB等粉末,在取得淨化溶液後,取2μl該溶液(也就是樣品檢液)滴在如前所述之SERS基板(320nm;銀奈米柱結構),等待乾燥,直至農藥分子吸附在該銀奈米柱結構上,再以2μl的甲醇:去離子水(1:1,v/v)混合液(也就是高揮發有機溶劑)滴附於SERS基板使農藥分子復溶,並先以波長808nm、功率200mW~300mW的紅外線雷射光照射該SERS基板,使有機溶劑快速揮發,留下濃縮的農藥分子,再以波長785nm、功率100mW的紅外線雷射光照射該SERS基板,使濃縮的農藥分子進一步深層吸附在銀奈米柱結構上,完成檢品的製備。最後再進行拉曼光譜量測,其中雷射光係採用785nm之波長、使用功率為100mW、透鏡倍率4X、積分時間為500ms、平均次數為32次。由光譜圖可知,其主要特徵峰值位於983cm-1,1004cm-1係三落松標準分子之主要位置,而1044cm-1、1224cm-1、1569cm-1為芬殺松農藥標準分子之主要位置,其拉曼峰之強度可做為農藥殘留半定量之判定依據。因此,本發明亦可同時用來檢測農作物上之多種農藥殘留。 The fifteenth figure shows the Raman detection spectrum of pesticides such as Triazophos and Fenthion remaining in wet rice. In general, after drying and dehulling, the concentration of pesticide residues in brown rice and white rice will be much less than 5 ppm. Therefore, in this experiment, the test sample is added with 5 ppm of trilopine in wet rice. (Triazophos) and 5 ppm of Fenthion. First, after mixing the above 10 g test sample with 10 ml of acetone, hand-shake for 30 seconds and take out 1 ml of the extraction solution through a purification column, and the PSA, C18, MgSO4, and GCB powders are simultaneously added to the purification column to obtain a purification solution. After that, 2 μl of the solution (that is, the sample test solution) was dropped on the SERS substrate (320 nm; silver nano column structure) as described above, and waited for drying until the pesticide molecules were adsorbed on the silver nano column structure, and then 2μl of methanol: deionized water (1:1, v/v) mixture (that is, high volatile organic solvent) is attached to the SERS substrate to re-dissolve the pesticide molecules, and firstly use infrared ray with a wavelength of 808nm and a power of 200mW~300mW. The SERS substrate is irradiated with light to rapidly evaporate the organic solvent, leaving concentrated pesticide molecules, and then irradiating the SERS substrate with infrared laser light having a wavelength of 785 nm and a power of 100 mW, so that the concentrated pesticide molecules are further deeply adsorbed on the silver nano column structure. , the preparation of the finished product. Finally, Raman spectroscopy is performed, in which the laser light system adopts a wavelength of 785 nm, a power of 100 mW, a lens magnification of 4×, an integration time of 500 ms, and an average number of times of 32 times. It can be seen from the spectrogram that the main characteristic peak is located at the main position of the standard molecule of 983cm-1, 1004cm-1, and 1044cm-1, 1224cm-1, and 1569cm-1 are the main positions of the standard molecules of Fenicide. The intensity of the Raman peak can be used as the basis for the semi-quantitative determination of pesticide residues. Therefore, the present invention can also be used to detect a plurality of pesticide residues on crops.

無論如何,任何人都可以從上述例子的說明獲得足夠教導,並據而了解本發明內容確實不同於先前技術,且具有產業上之利用性,及足具進步性。是本發明確已符合專利要件,爰依法提出申請。 In any event, anyone can obtain sufficient teaching from the description of the above examples, and it is understood that the present invention is indeed different from the prior art, and is industrially usable and progressive. It is the invention that has indeed met the patent requirements and has filed an application in accordance with the law.

1‧‧‧表面增強型拉曼散射基板 1‧‧‧ Surface-enhanced Raman scattering substrate

11‧‧‧矽基板 11‧‧‧矽 substrate

12‧‧‧金屬奈米或微米結構 12‧‧‧Metal nano or micro structure

2‧‧‧雷射光源 2‧‧‧Laser light source

3‧‧‧拉曼光譜儀 3‧‧‧Raman Spectrometer

Claims (10)

一種表面增強型拉曼光譜檢測方法,包括底下步驟:(a).對一待測樣品進行萃取及淨化,形成一樣品檢液;(b).將萃取淨化後之樣品檢液滴附在一SERS基板,以使該樣品檢液之化學分子吸附於該SERS基板上;(c).續以高揮發性之有機溶劑滴附於前述吸附有化學分子之SERS基板上,以使化學分子復溶於該有機溶劑中,進而浮出該SERS基板表面;(d).以光照射該SERS基板,以使該SERS基板上之有機溶劑受熱揮發,而留下之化學分子則逐漸集中至一濃縮區域;(e).再以雷射光照射該濃縮區域,以使該濃縮區域中之化學分子較深層地吸附於該SERS基板,藉以形成固相的一光譜量測區;及(f).以雷射光聚焦於該光譜量測區,進行拉曼光譜量測。 A surface enhanced Raman spectroscopy method comprising the following steps: (a) extracting and purifying a sample to be tested to form a sample test solution; (b) attaching the sample to the sample after extraction and purification a SERS substrate for adsorbing chemical molecules of the sample liquid on the SERS substrate; (c) continuing to immerse the highly volatile organic solvent on the SERS substrate on which the chemical molecules are adsorbed to reconstitute the chemical molecules In the organic solvent, the surface of the SERS substrate is floated; (d) the SERS substrate is irradiated with light to cause the organic solvent on the SERS substrate to be volatilized by heat, and the remaining chemical molecules are gradually concentrated to a concentrated region. (e) further irradiating the concentrated region with laser light such that chemical molecules in the concentrated region are more deeply adsorbed on the SERS substrate, thereby forming a spectral measurement region of the solid phase; and (f). The illuminating light is focused on the spectral measurement area for Raman spectroscopy. 如申請專利範圍第1項所述之,其中步驟(a)中進行萃取所使用之萃取溶劑係選自丙酮、甲醇、乙腈及含醋酸之乙腈溶液所組成之群組。 As described in claim 1, the extraction solvent used in the step (a) is selected from the group consisting of acetone, methanol, acetonitrile and an acetic acid-containing acetonitrile solution. 如申請專利範圍第1項所述之,其中步驟(a)中所進行之淨化係使萃取後之待測液依序通過一淨化管柱以及一微米孔徑之濾膜。 As described in the first aspect of the patent application, the purification performed in the step (a) is such that the liquid to be tested after the extraction passes through a purification column and a filter membrane of a micrometer aperture. 如申請專利範圍第1項所述之表面增強型拉曼光譜檢測方法,其中步驟(c)中所使用之該高揮發性的有機溶劑係由丙酮、甲醇及乙醇中之至少一者稀釋而成。 The method of surface-enhanced Raman spectroscopy according to claim 1, wherein the highly volatile organic solvent used in the step (c) is diluted with at least one of acetone, methanol and ethanol. . 如申請專利範圍第4項所述之表面增強型拉曼光譜檢測方法,其中用來稀釋成該高揮發性之有機溶劑的稀釋劑包括去離子水、乙腈及甲醇中之任一者。 The surface enhanced Raman spectroscopy method according to claim 4, wherein the diluent for diluting to the highly volatile organic solvent comprises any one of deionized water, acetonitrile and methanol. 如申請專利範圍第5項所述之表面增強型拉曼光譜檢測方法,其中步驟(d)中所使用的光係紅外線,其波長介於760nm~2000nm,且其光源之輸出功率大於1mW;而步驟(e)中所使用的雷射光之波長介於760nm~1500nm,且其光源之輸出功率不大於500mW。 The surface enhanced Raman spectroscopy method according to claim 5, wherein the light-based infrared light used in the step (d) has a wavelength of 760 nm to 2000 nm, and an output power of the light source is greater than 1 mW; The wavelength of the laser light used in the step (e) is between 760 nm and 1500 nm, and the output power of the light source is not more than 500 mW. 如申請專利範圍第6項所述之表面增強型拉曼光譜檢測方法,其中步驟(e)中所使用之紅外線係選用單一波長的雷射光。 The surface enhanced Raman spectroscopy method according to claim 6, wherein the infrared ray used in the step (e) is a single wavelength laser light. 一種化學物質濃縮方法,包括底下步驟:(a).將一樣品檢液滴附在一金屬基板,以使該樣品檢液之化學分子吸附於該金屬基板上;(b).續以高揮發性之有機溶劑滴附於前述吸附有化學分子之金屬基板上,以使化學分子復溶於該有機溶劑中,進而浮出該金屬基板表面;及(c).使該金屬基板上之有機溶劑受熱揮發,留下之化學分子逐漸集中至一濃縮區域。 A method for concentrating a chemical substance, comprising the following steps: (a) attaching a sample to a metal substrate to adsorb chemical molecules of the sample liquid on the metal substrate; (b) continuing to be highly volatile The organic solvent is dropped on the metal substrate on which the chemical molecule is adsorbed, so that the chemical molecule is redissolved in the organic solvent to float the surface of the metal substrate; and (c) the organic solvent on the metal substrate It is volatilized by heat, and the remaining chemical molecules are gradually concentrated to a concentrated area. 如申請專利範圍第8項所述之化學物質濃縮方法,其中步驟(c)係以較低能量之紅外線照射於該金屬基板上,以使該金屬基板上之有機溶劑快速揮發。 The method of concentrating a chemical substance according to claim 8, wherein the step (c) is irradiated onto the metal substrate with a lower energy infrared ray to rapidly evaporate the organic solvent on the metal substrate. 如申請專利範圍第9項所述之化學物質濃縮方法,更包括在步驟(c)之後,續以較高能量之紅外線雷射光照射該濃縮區域,使化學分子更加緊密地吸附於該金屬基板上。 The method for concentrating a chemical substance according to claim 9, further comprising, after the step (c), irradiating the concentrated region with a higher energy infrared laser light to more closely adsorb the chemical molecules on the metal substrate. .
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