TW200526951A - Opto-electrochemistry detection method and the apparatus thereof - Google Patents

Opto-electrochemistry detection method and the apparatus thereof Download PDF

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TW200526951A
TW200526951A TW93103237A TW93103237A TW200526951A TW 200526951 A TW200526951 A TW 200526951A TW 93103237 A TW93103237 A TW 93103237A TW 93103237 A TW93103237 A TW 93103237A TW 200526951 A TW200526951 A TW 200526951A
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patent application
copper
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TW93103237A
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TWI251672B (en
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zhi-ming Ceng
Xie-Xun Zhong
Zhen-Teng Xu
xue-hui Yang
Mei-Xin Qiu
Jun-Wei Su
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Chan Pu Technology Co Ltd
zhi-ming Ceng
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Abstract

The present invention relates to an opto-electrochemistry detection method and the apparatus thereof. The method is to further combine an electrode made of opto-electrochemistry material in the electrochemistry detector, and employ the irradiation to enhance the current to increase the detection precision, and enhance the sensitivity of the detector. The apparatus according to the present invention comprises a base, a cover pivoted on the base, and a locking device configured between the base and the cover, and the top of the base is formed with an accommodation slot for accommodating the semi-conductive electrode sheet; and, the cover is provided with a ring slot corresponding to the electrode sheet; a washer accommodated in the ring slot; a light hole with a transparent glass, and a plurality of flow holes connecting the outside and the ring slot; and, when the cover is tightly combined on the substrate, the washer will form a detection space between the cover and the base; next, injecting the detected solution from the flow hole to the detection space, and connecting the current and irradiating suitable light through the light holes to excite the transformation of opto-electronic substance on the semiconductor electrode, and employing the opto-electric current generated during transformation to enhance the sensitivity for detection analysis. Moreover, the apparatus has a feature that it could easily open the cover to replace with new electrode sheet to be an opto-electrochemistry detection device with simple and easy operation.

Description

200526951 玖、發明說明: 【發明所屬之技術領域】 本發明係關於一種光電化學檢測方法及其裝置,特別 是一種應用於銅網版印刷電極領域、可增強檢測靈敏=與 便利性之流體光化學電流檢測方法及其裝置者。 〃 【先前技術】 電化學檢測器是化學研究中新興的領域,其學術價值 及經濟效益都非常地可觀《檢測器的製造涉及許多學門之 專業知識,幾乎涵蓋了理…農、醫各領域,而;分析 化學更是當中的核心研究。一般檢測器需具備優良的選擇 性、高靈敏度及較短的偵測時間,若能兼具良好的稃定性 與可靠性,其主要發展空間’在於與流動注入系統⑺⑽ Injection Analysis,FIA )、液相層析分離法( Performance Liquid Chromat〇graphy,HpLc )、或毛細管電 冰分離技術(Capillary Electroph〇resis,CE)結合,其偵 檢之靈敏度可實際應用於解決生醫與環保相關的:手二析200526951 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a photoelectrochemical detection method and its device, in particular to a fluid photochemistry applied to the field of copper screen printing electrodes, which can enhance detection sensitivity = and convenience Current detection method and device thereof.先前 [Previous technology] Electrochemical detectors are an emerging field in chemical research, and their academic value and economic benefits are very considerable. "The manufacture of detectors involves many disciplines of professional knowledge, covering almost all fields of science, agriculture, and medicine. And; analytical chemistry is the core research among them. Generally, the detector needs to have excellent selectivity, high sensitivity, and short detection time. If it can have both good characterization and reliability, its main development space is' with the flow injection system ⑺⑽ Injection Analysis (FIA), liquid Combining phase chromatography (Performance Liquid Chromatography, HpLc), or capillary electro-ice separation technology (Capillary Electrophoresis, CE), the detection sensitivity can be practically used to solve the problems related to biomedicine and environmental protection: hand two Analyze

問題。 丁刀W 【發明内容】 、由於目前傳統的電化學檢測器,在檢測方面的靈敏度 並不佳’同時尚未有便利且完整的裝置來操作,因此,本 發明人經過努力研究與開發,以研發出__種結合與斑 電化子之新賴光電化學檢測方法及可應用該方法了 以期增加液體檢測之準確性。 t ,ΐΠ:之?要目的係在於提供一種光電化學檢測方法 八α L達到提高流體之檢測靈敏度之目的。 200526951 本發明之另一主要目的係在於提供一種流體電化學檢 測裝置,其可以實施上述之光電化學檢測方法,並能達到 簡易地替換檢測電極之目的。 為達到上述的目的,本發明之光電化學檢測方法主要 係為: 在一電化學檢測器中結合光電化學材質之電極,利用 照光的方式產生光電流以增強一檢測液體中的檢測電流, 以提局檢測之準確度。 為達到上述的另一目的,本發明之光電化學檢測裝置 其主要結構係包含有: 一基座’其具有一頂面、一前端與一後端,基座頂面 形成有一延伸至前端之容置槽; 一樞設於基座後端之蓋體,該蓋體具有一頂面、一底 面、一前端、一後端與兩側邊,蓋體底面形成有一具有内 開口,並對應容置槽之彈性分隔體,一光照孔與複數個流 孔形成於蓋體上並連通至分隔體之内開口範圍内; 一放置於容置槽中的檢測電極,該檢測電極對應光照 孔的位置上形成有具光電轉換性質之半導體材料;與 一設置於基座與蓋體之間之卡扣裝置。 其中卡扣裝置包含有: 兩個形成於基座頂面、含有定位珠之定位柱;盘 一形成於蓋體前端上、對應定位珠之珠槽。〃 藉此,本發明利用照光的方# 々环配合光電化學材皙之 電極,以增強檢測液體中的電流, 、 乂杈同彳欢測之準確度; 200526951 而在裝置“’制蓋體光照孔的言史置與具有&電轉換性 質之半導體檢測電極的使用’以達到產生光化學電流增加 檢測裝置的靈敏度的優㉟,另一方面,基座與蓋體之二的 樞設與卡扣裝置的設置’輕易的開啟蓋體以重新替換新的 檢測電極試片,讓檢測更為簡易便利者。 【實施方式】problem. Ding W [Summary of the invention] [Due to the current traditional electrochemical detectors, the detection sensitivity is not good 'and there is no convenient and complete device to operate. Therefore, the inventors have worked hard on research and development to develop A new photoelectrochemical detection method combining __ with spotted chemokines and the method can be applied in order to increase the accuracy of liquid detection. t, ΐΠ: Which? The main purpose is to provide a photoelectrochemical detection method to achieve the purpose of improving the detection sensitivity of the fluid. 200526951 Another main object of the present invention is to provide a fluid electrochemical detection device which can implement the above-mentioned photoelectrochemical detection method and can achieve the purpose of easily replacing the detection electrode. In order to achieve the above-mentioned object, the photoelectrochemical detection method of the present invention is mainly as follows: combining an electrode of photoelectrochemical material in an electrochemical detector, and generating a photocurrent by irradiating light to enhance a detection current in a detection liquid to improve The accuracy of the local inspection. In order to achieve the above-mentioned another object, the main structure of the photoelectrochemical detection device of the present invention includes: a base 'having a top surface, a front end, and a rear end, and the top surface of the base has a capacity extending to the front end. A slot pivotally arranged at the rear end of the base, the cover having a top surface, a bottom surface, a front end, a rear end and two sides, the bottom surface of the cover is formed with an internal opening and correspondingly accommodated An elastic separator of the slot, a light hole and a plurality of flow holes are formed on the cover and communicate with the inner opening of the separator; a detection electrode placed in the containing slot, and the detection electrode is at a position corresponding to the light hole. A semiconductor material with photoelectric conversion properties is formed; and a buckle device disposed between the base and the cover. The buckle device includes: two positioning posts formed on the top surface of the base and containing positioning beads; and a disk formed on the front end of the cover body and corresponding to the bead grooves of the positioning beads. 〃 In this way, the present invention utilizes the square of the light to match the electrode of the photoelectrochemical material to enhance the accuracy of detection of the current in the liquid, and the accuracy of the measurement; The history of holes and the use of semiconductor detection electrodes with electrical conversion properties' to achieve the superiority of generating a photochemical current to increase the sensitivity of the detection device. On the other hand, the pivot and the card of the base and the cover are two. Setting of the buckle device'Easily open the cover to replace the new test electrode test strip, making testing easier and more convenient. [Embodiment]

本發明之光電化學檢測方法中,其主要為在一電化學 檢測器中結合光電化學材質之電極,利用照光的方式產I 光電流以增強一檢測液體中的檢測電流,以提高檢測之準 確度。 本發明中作為電極使用之光電化學材料可以為銅、銀 、金等金屬之合金或衍生物,其中特別為銅合金方面例如 有銅鉑合金(CuPt)、銅鈀合金(CuPd)、銅汞合金(Cu{{g)、 銅銀合金(CuAg)、與銅金合金(CuAu)等等;其中特別為銅 的衍生物方面為氣化銅(CuC1)、溴化銅(CuBr)、碘化銅 (Cul)、氧化銅(Cu0)、氟化銅(CuF)、鈪化銅(CuAt)、或氧 化二銅(ChO)等等。其中Cu/o和Cun〇為較佳之選擇,其 方法原理說明如下:In the photoelectrochemical detection method of the present invention, it is mainly combined with an electrode of photoelectrochemical material in an electrochemical detector, and the I photocurrent is generated by the way of light to enhance the detection current in a detection liquid to improve the accuracy of detection. . The photoelectrochemical material used as an electrode in the present invention may be an alloy or derivative of copper, silver, gold and other metals. Among them, copper alloys include, for example, copper platinum alloy (CuPt), copper palladium alloy (CuPd), and copper amalgam. (Cu {{g), copper-silver alloy (CuAg), and copper-gold alloy (CuAu), etc .; among them, copper derivatives in particular are vaporized copper (CuC1), copper bromide (CuBr), copper iodide (Cul), copper oxide (Cu0), copper fluoride (CuF), copper halide (CuAt), or copper oxide (ChO), etc. Among them, Cu / o and Cun〇 are better choices. The principle of the method is described as follows:

Cu20和Cun0都是半導體材料(Semiconductor)並 具有光電化學的性質,如Cu/O是屬於具有多電洞(h+ ) 之P型半導體材料(p-semiconductor),其電子躍遷的能 階差(Band gap)大約是1· 5- 2· 0 eV,可吸收的光波長 範圍大約是500 — 600 nm左右,因此常被用作為銅網版印 刷電極(CuSPE)之材料,讓CuSPE具有光電轉換現象。 200526951 簡單以下列反應式表現cwpE在光電化學之反應機制Cu20 and Cun0 are both semiconductor materials and have photoelectrochemical properties. For example, Cu / O is a p-semiconductor material with multiple holes (h +), and its energy transition (band) The gap) is about 1.5-2.0 eV, and the wavelength range of light that can be absorbed is about 500-600 nm. Therefore, it is often used as a material for copper screen printing electrodes (CuSPE), so that CuSPE has a photoelectric conversion phenomenon. 200526951 Express the reaction mechanism of cwpE in photoelectrochemistry simply by the following reaction formula

CuSPE的光電化學反應機構推演 當Cu與Cun0吸收光能時,具有半導體性質的Cu2i〇 也因應而生,並且在持續照光之下形成激發態物種( Cu/O*),以及氧化電位(A)的控制下,可得氧化的光電 化學電流(Photoelectrochemical current,/pEc);此時 若有易傳遞電子(Electron donor )之分析物,如兒茶酚 (Catechol,CA)等,可提供電子給Cu2l〇*使之回到基態( Cii/O),因此若以此銅網版印刷電極(CuSpE)應用於電化 學檢測器,持續照光與氧化電位控制之下,產生更大的光 電流,因此對傳統的電化學檢測器而言,應用光電轉換產 生放大性光電流,可大大提升電化學檢測器偵測的分析訊 號之靈敏度。 關於光電化學檢測裝置方面,請參考第一圖與第二圖 ’其結構中包括有一基座(10)、-樞設於基座上之蓋 一(y 0 ) 一形成於盍體(2 0 )上之光照孔(2 2 ) 可抽換之光電半導體檢測電極(5 0 ),與-裝設於 土 “( 1 0 )肖盍體(2 〇 )之間的卡扣裝置(未標號) 200526951 基座(1 〇)為一四方形塊體,其具有一頂面、四個 側邊 别端與一後端,基座(1 〇 )頂面形成有一延伸 至财端之長條狀容置槽(1 2 ),並於靠近後端處形成有 才區柱(1 1 ),此外,基座(1 Q )四個側邊上設有複 數這止滑刻痕(1 0 2 ),較佳地,該容置槽(1 2 )為 一定位效果較好的鸠尾槽。 蓋體(2 〇 )係樞設於基座(1 〇 )上,該蓋體(2 0 )為一方形塊體,其具有一頂面、一底面、一前端、一 後端與兩側邊,蓋體(2 0 )前端兩側各形成一肩槽(未 ^號)’蓋體(20)底面可形成有一具有内開口(未標 说)之彈性分隔體(未標號),複數個流孔形成於蓋體上 並連通至分隔體之内開口範圍内,較佳地,如圖中所示, 盖體底面上形成有一環槽(28),環槽(28)内容置 有一具作為分隔體之彈性方型墊圈(2 8 2 ),一光照孔 (22)形成於蓋體(2〇)之頂面並連通至墊圈(28 2)圈住之範圍内,另有一第一流出孔(24)與一第二 流出孔(2 6 )分別形成與蓋體(2 〇 ) —側邊,並有一 /主入孔(27)形成與蓋體(2〇)另一側邊,同樣連通 至墊圈(2 8 2 )所圈住之範圍内。蓋體(2 〇 )後端形 成有一凹槽(2 1 ),該凹槽(2 1 )可對應容置基座( 1 0 )樞柱(1 1 ),並以一樞軸(丄i丄)穿設過蓋體 (2 0 )凹槽(2 1 )兩側與樞柱(1 1 ),藉此將蓋體 (2 0 )與基座(1 〇 )樞設連結。請進一步配合參考第 200526951 三圖,光照孔(2 2 )中在靠近蓋體 〇 )底面處形成 有一限止環(2 2 2 ) 並有一透光破螭(2 2 4 )底靠 於限止謂22)上’當蓋體(2〇)下壓貼合基座( 10)時’塾圈(282)會在蓋體(2〇)與基座(1 0 )之間間隔出一檢測空間(a )。 卡扣裝置係設置於基座(1 〇 )與蓋體(2 〇 )之間 以將兩者緊密結合在一起,其包含有兩個形成於基座(工 0 )頂面、含有定位珠(1 8 6 )之定位桎(i 4 )與一 形成於蓋體(2 0 )前端上、對應定位珠(i 8 6 )之珠 槽(23),當基座(1〇)與蓋體(2〇)蓋合時,每 一定位柱(1 4 )係對應於蓋體(2 〇 )每一肩槽之位置 ’而珠槽(2 3 )設於肩槽内,較佳地,定位柱(1 4 ) 内部形成有一螺孔(1 4 2 )’並有-調節螺桿(丄8 ) 栓設於螺孔(1 4 2 )内,調節螺桿(丄8 )轴向形成一 轴孔(182),並在軸孔(182)中容置設有一頂持 於定位珠(;L 8 6 )上的彈性體(i 8 4 ),藉由彈性體 (1 8 4 )的彈力作用將定位珠(丄8 6 )壓迫推向珠槽 (2 3 )以提供卡掣的效果,其_調節螺栓(i 8 )可以 依鎖入螺孔(1 4 2 )中的深度來調節卡扣元件之緊度。 較佳地,該彈性體(1 8 4 )為一彈簧。當蓋體(2 〇 ) 貼合座體(1 0 )時’定位珠(1 8 6 )會卡擎於珠槽( 23)中,以固定住蓋體(2〇)於座體(1〇)上讓 墊圈(2 8 2 )緊壓於基座(χ 〇 )上形成檢測空間(a ),當開啟盍體(2 0 )時,只須施力讓定位珠(丄8 6 200526951 )推動彈性體(1 8 4 )以脫離珠槽(2 3 )即可,因此 ,對於開啟或關閉蓋體(2〇)都相當簡便。 檢測電極(5 〇 )係為置於容置槽(丄2 )内,其長 度:大於容置槽(12),朝上面具有一對應環槽(28 )X置的内接點(5 2 ),並設有—連接—讀取裝置的外 接(5 4 )’该内接點(5 2 )上須要形成一層具有光 電轉換性質之半導體材料,如氧化亞銅等。 卜吻參考第一圖與第四圖,本發明之光電化學檢 測裝置’須要在蓋體(2 〇 )關閉之後,自注入孔(2 7 )注入流體並從第一或第二流出孔(2 4 ) ( 2 8 )導出 流體’當檢測時在檢測電極上接通一冑當電廢,並以一發 光源(5 5 )穿入照光孔(2 2 )巾,透過照光孔(2 ^ )”透光玻ί离(2 2 4 ) ’讓光能進入檢測空間(a ), 激發檢測電極(50)内接點(52)上的半導體材料產 生光化學電流,以放大電流檢測之反應,增加檢測裝置的 靈敏度。 此外,本發明之光電化學檢測裝置可依需要配合使用 參考電極或輔助電極連接於第一流出孔(2 4 )或第二流 出孔(2 6 )使用,以增加檢測器之操作變化性。 為了證明本發明中光電化學檢測方法之效果,以下為 一測試實驗:利用上述之自製光電化學檢測裝置,進行對 於苯鄰二酚類化合物(〇HPs )的偵測,首先針對照光與光 源強度對整個實驗的影響做評估。 “ 請參照第五圖所示,為以安培伏安法在F丨 示騎> 中配 12 200526951 合150 W鹵素燈(Halogen lamp)照射以偵測OHPs的結 果。前300秒未施加光源(Light off),注入100 μΜ CA 時的電流訊號為0· 33 μΑ。300秒之後開始將光源依次以 不同的強度打開(on — a,-b,-c和max· -d ),並在不同光 源強度之下,也分別注入1 〇〇 μΜ CA。由圖中發現,每當 光源更強時其背景光電流(Background photocurrent )也 · 就更大,這也更證明了中所推測的光電化學反應的機構, 亦即背景光電流是由價帶(VB )的電子被激發後,流向電 極方向的光電化學電流(/PEC )所致。同時,隨著背景光參 電流地增加,所注入的CA電流訊號也跟著增加放大,由 第六圖的線性回歸線(B圖)上,可以更清楚看出其改變 趨勢,以實驗室目前的150 W鹵素燈(Halogen iamp), 可以將CA的偵測電流最大增加至267 %,而且增大的電流 也尚未飽和。相信若使用更大功率的光源,一定可以再增 加偵測的靈敏度。此外,本發明已經過美國分析化學期刊 的認證其正確性,並獲發表於2 〇 〇 3年1 2月1 5曰美 國分析化學期刊中(内容詳見附件)。 _ 綜上所述,本發明由於藉由光照與具有光電轉換性質 之半導體檢測電極(5 0 )的使用,以達到產生光化學電 流增加檢測裝置的靈敏度的優點,另一方面,裝置中基座 與盍體之間的樞設與卡扣裝置的設置,可以輕易的開啟戋 結合蓋體,以重新替換基座上之檢測電極試片,因此具有 操作簡易便利之的特性,以簡化檢驗操作,具有相當的進 V f生、貫用性及產業利用性,符合發明專利申請要件,因 13 200526951 此具文提出發明專利申請。 【圖式簡單說明】 (一)圖式部分 第圖·係為本發明之立體分解圖。 第一圖:係為本發明呈閉闔狀態之上面剖視圖。 第三圖··係為本發明沿第二圖中3 一 3線之前側 剖視圖。 第四圖·係為本發明沿第二圖中4 — 4線之操作 狀態側面剖視圖。CuSPE's photoelectrochemical reaction mechanism deduces that when Cu and Cun0 absorb light energy, Cu2i0 with semiconductor properties also emerges, and forms excited species (Cu / O *) and oxidation potential (A) under continuous illumination. The photoelectrochemical current (/ pEc) can be obtained under the control of oxidant; at this time, if there is an analyte that easily transfers electrons (such as Catechol, CA), the electron can be provided to Cu2l 〇 * Return it to the ground state (Cii / O). Therefore, if this copper screen printing electrode (CuSpE) is applied to an electrochemical detector, it will continue to be under the control of light and oxidation potential to generate a larger photocurrent. For traditional electrochemical detectors, the use of photoelectric conversion to generate amplified photocurrents can greatly increase the sensitivity of the analytical signals detected by the electrochemical detectors. Regarding the photoelectrochemical detection device, please refer to the first figure and the second figure. The structure includes a base (10), a cover (y 0) pivotally formed on the base, and a body (2 0). The light hole (2 2) above can be replaced by a photoelectric semiconductor detection electrode (50), and a snap-in device (not labeled) installed between the soil "(10) and the Xiao body (20). 200526951 The base (10) is a quadrangular block, which has a top surface, four lateral ends and a rear end. The top surface of the base (10) has a long shape extending to the wealth end. A groove (1 2) is formed, and a talent column (1 1) is formed near the rear end. In addition, the four sides of the base (1 Q) are provided with a plurality of anti-slip marks (1 0 2), Preferably, the receiving groove (12) is a dovetail groove with better positioning effect. The cover body (20) is pivotally arranged on the base (10), and the cover body (20) is one side. Block, which has a top surface, a bottom surface, a front end, a rear end, and two sides, and a shoulder groove (not ^) is formed on each side of the front end of the cover body (20), and the bottom surface of the cover body (20) May be formed with an internal opening (not Said) elastic separator (not labeled), a plurality of flow holes are formed on the cover and communicate with the inner opening of the separator. Preferably, as shown in the figure, a ring groove is formed on the bottom surface of the cover ( 28), an elastic square washer (2 8 2) as a separator is placed in the ring groove (28), and a light hole (22) is formed on the top surface of the cover (20) and communicates with the washer (28 2 ) Within the bounding range, another first outflow hole (24) and a second outflow hole (2 6) are respectively formed with the cover body (20)-side, and a / main access hole (27) is formed with The other side of the cover body (20) is also connected to the range surrounded by the gasket (2 8 2). A groove (2 1) is formed at the rear end of the cover body (20), and the groove (2 1) ) Can correspondingly receive the pivot (1 1) of the base (1 0), and a pivot (丄 i 丄) is passed through both sides of the groove (2 1) of the cover (2 0) and the pivot (1 1), so as to pivotally connect the cover (20) with the base (10). Please further refer to the third figure of 200526951, a limit is formed in the illumination hole (2 2) near the bottom surface of the cover (0). Ring (2 2 2) and there is a penetration Break the bottom (2 2 4) against the limit 22) 'When the cover (20) is pressed against the base (10), the ring (282) will be between the cover (2) and the base A detection space (a) is separated between (10). The buckle device is arranged between the base (10) and the cover (20) to tightly combine the two, which includes two A positioning groove (i 4) formed on the top surface of the base (work 0), containing positioning beads (1 8 6), and a bead groove formed on the front end of the cover (20), corresponding to the positioning beads (i 8 6) (23) When the base (10) and the cover (20) are closed, each positioning post (1 4) corresponds to the position of each shoulder groove of the cover (20), and the bead groove ( 2 3) is provided in the shoulder groove, preferably, a screw hole (1 4 2) 'is formed inside the positioning post (1 4) and an adjusting screw (丄 8) is bolted in the screw hole (1 4 2) An axial hole (182) is formed in the axial direction of the adjusting screw (丄 8), and an elastic body (i 8 4) held on the positioning bead (; L 8 6) is accommodated in the axial hole (182). By the elastic force of the elastic body (1 8 4), the positioning beads (丄 8 6) are pressed and pushed toward the bead grooves (2 3) to provide For the effect of the latch, the _ adjusting bolt (i 8) can adjust the tightness of the latching element according to the depth locked into the screw hole (1 4 2). Preferably, the elastic body (1 8 4) is a spring. When the cover body (20) fits on the base body (10), the positioning beads (186) will be stuck in the bead grooves (23) to fix the cover body (20) on the base body (10). ) On the washer (2 8 2) on the base (χ 〇) to form a detection space (a), when the carcass (20) is opened, you only need to force the positioning beads (丄 8 6 200526951) to push The elastic body (1 8 4) can be detached from the bead groove (2 3). Therefore, it is quite easy to open or close the cover body (20). The detection electrode (50) is placed in the accommodating groove (丄 2), and its length is larger than the accommodating groove (12), and an inner contact point (5 2) corresponding to the ring groove (28) is arranged toward the upper side. An external connection (5 4) of the -connection-reading device is provided. A layer of semiconductor material with photoelectric conversion properties, such as cuprous oxide, must be formed on the internal connection point (5 2). With reference to the first figure and the fourth figure, the photoelectrochemical detection device of the present invention requires that after the cover (20) is closed, a fluid is injected from the injection hole (27) and the first or second outflow hole (2 4) (2 8) Export the fluid 'When testing, turn on the electric waste on the detection electrode, and pass a light source (5 5) into the light hole (2 2), and pass through the light hole (2 ^) "Translucent glass (2 2 4) 'Let light energy enter the detection space (a), excite the semiconductor material on the contact (52) inside the detection electrode (50) to generate a photochemical current to amplify the current detection reaction, Increase the sensitivity of the detection device. In addition, the photoelectrochemical detection device of the present invention can be used in conjunction with a reference electrode or an auxiliary electrode connected to the first outflow hole (2 4) or the second outflow hole (2 6) to increase the detector. In order to prove the effect of the photoelectrochemical detection method in the present invention, the following is a test experiment: using the self-made photoelectrochemical detection device described above to detect catechol compounds (〇HPs), first Light and light source intensity Effect Evaluation of the experiment do "Referring to Figure V, is in amps voltammetry shown in Shu F ride >. 12200526951 engagement with the 150 W halogen lamp (Halogen lamp) to detect the irradiation results OHPs. No light off was applied for the first 300 seconds, and the current signal when 100 μM CA was injected was 0.333 μA. After 300 seconds, the light source was turned on sequentially with different intensities (on — a, -b, -c, and max · -d), and under different light source intensities, 100 μM CA was also injected. It is found from the figure that whenever the light source is stronger, the background photocurrent (Background photocurrent) is larger, which also proves the mechanism of the photoelectrochemical reaction inferred in the figure, that is, the background photocurrent is caused by the valence band ( VB) is caused by the photoelectrochemical current (/ PEC) flowing in the direction of the electrode. At the same time, as the background light parameter current increases, the injected CA current signal also increases and enlarges. From the linear regression line in Figure 6 (Figure B), the change trend can be seen more clearly. W halogen lamp (Halogen iamp), can increase the detection current of CA up to 267%, and the increased current is not yet saturated. It is believed that if a more powerful light source is used, the detection sensitivity can be increased. In addition, the present invention has been certified by the American Journal of Analytical Chemistry for its correctness and was published in the American Journal of Analytical Chemistry on December 15th, 2003 (see the attachment for details). _ In summary, the present invention achieves the advantage of increasing the sensitivity of the detection device by generating a photochemical current due to the use of light and the use of a semiconductor detection electrode (50) with photoelectric conversion properties. On the other hand, the base of the device The pivotal connection with the carcass and the setting of the buckling device can easily open the carcass and combine the cover to replace the test electrode test strip on the base, so it has the characteristics of simple and convenient operation to simplify the inspection operation. It has considerable production, consistency, and industrial applicability, which meets the requirements for patent application for inventions. Because of this, the application for invention patents is filed in this article. [Brief description of the drawings] (I) Schematic drawing The figure is an exploded perspective view of the present invention. The first figure is a top sectional view of the present invention in a closed state. The third figure ... is a sectional view of the present invention taken along the line 3-3 in the second figure. The fourth figure is a side sectional view of the present invention in an operating state taken along line 4-4 in the second figure.

第五圖:係為偵測〇HPs操作實驗結果之時間、 光照強度與輸入電流大小對應所偵測電流強度之對照曲線 圖(A )與長條圖(b )。 第六圖:係為偵測〇HPs操作實驗中照光或不照 光的情形下’時間與輸入電流大小對應所偵測電流強度之 對照曲線圖(A )與線性回歸圖(b )。 (二)元件代表符號 (1 0 )基座 (1 1 )彳區柱 (1 1 1 )樞軸 (1 4 )定位柱 (1 8 )調節螺桿 (1 8 4 )彈性體 (2 0 )蓋體 (2 2 2 )限止環 (1 0 2 )止滑刻痕 (12)容置槽 (1 4 2 )螺孔 (1 8 2 )軸孔 (1 8 6 )定位珠 (2 2 )光照孔 (2 2 4 )透光玻璃Fifth graph: It is a control curve (A) and a bar graph (b) of the time, light intensity and input current corresponding to the detected current intensity for detecting the results of the 0HPs operation experiment. Figure 6: The control curve (A) and linear regression graph (b) of the time and input current corresponding to the intensity of the detected current in the case of detecting light or no light during the operation test of 0HPs. (2) Symbols for component representation (1 0) Base (1 1) Column (1 1 1) Pivot (1 4) Positioning column (1 8) Adjusting screw (1 8 4) Elastomer (2 0) cover Body (2 2 2) stop ring (1 0 2) anti-slip nick (12) receiving groove (1 4 2) screw hole (1 8 2) shaft hole (1 8 6) positioning bead (2 2) light hole (2 2 4) Transparent glass

14 200526951 (2 3 )珠槽 (2 4 )第一流出孔 (2 6 )第二流出孔 (2 7 )注入孔 (2 8 )環槽 (2 8 2 )〇型環 (3 0 )參考電極 (3 2 )螺桿 (3 4 )第二金屬桿 ^ (4 0 )輔助電極 (4 2 )螺桿 (4 4 )第一金屬桿 (5 0 )檢測電極 (5 0 a )檢測電極 @ (5 2 )内接點 (5 4 )外接點 (a )檢測空間 (三)附件 本發明於2 0 0 3年1 2月1 5曰美國分析化學期刊 第75冊第24卷,第7020—7025頁所發表之公 開本。(網路公開曰期為2 0 0 3年1 1月1 5曰) 1514 200526951 (2 3) Bead groove (2 4) first outflow hole (2 6) second outflow hole (2 7) injection hole (2 8) ring groove (2 8 2) o-ring (3 0) reference electrode (3 2) screw (3 4) second metal rod ^ (4 0) auxiliary electrode (4 2) screw (4 4) first metal rod (5 0) detection electrode (50 0 a) detection electrode @ (5 2 ) Inner point (5 4) Outer point (a) Detection space (3) Attachment The present invention was published on February 15th, 2003. The American Journal of Analytical Chemistry, Volume 75, Volume 24, pages 7020-7025 Published public version. (The date of online publication is 2003, January 1 and January 15) 15

Claims (1)

200526951 拾、申請專利範圍: 1 · 一種光電化學檢測方法,其主要為在一電化學檢 測&中、结合光電化學材質之電極,利用照光的方式產生光 電流以增強一檢測液體中的檢測電流,以提高檢測之準確 度及靈敏度。 — 2 ·如申請專利範圍第1項所述之光電化學檢測方法 · ’其中電極材料為銅合金,其係選自下列群組包含有··銅 祐合金、銅把合金、銅汞合金、銅銀合金與銅金合金。 3 ·如申請專利範圍第1項所述之光電化學檢測方法 籲 ’其中電極材料為銅的衍生物,其係選自下列群組包含有 •氣化銅/臭化銅、埃化銅、氧化銅、氟化銅、鈪化銅和氧 化二銅。 4 ·如申請專利範圍第2項所述之光電化學檢測方法 ’其中電極材料為一價銅氧化物。 5 ·如申請專利範圍第2項所述之光電化學檢測方法 ’其中電極材料為二價銅氧化物。 6 · —種光電化學檢測裝置,其結構包括有: 春 一基座,其具有一頂面、一前端與一後端,基座頂面 形成有一延伸至前端之容置槽; 一樞設於基座後端之蓋體,該蓋體具有一頂面、一底 面 刚鳊、一後端與兩側邊,蓋體底面形成有一具有内 開口,並對應容置槽之彈性分隔體,一光照孔與複數個流 孔形成於k體上並連通至分隔體之内開口範圍内; 一放置於容置槽中的檢測電極,該檢測電極對應光照 16 200526951 孔的位置上形成有豆弁/^絲德卩研 . X ’八尤电轉換性質之半導體材料;與 一設置於基座與蓋體之間之卡扣裝置。 、 7 .如申請專利範圍第6項之光電化學檢測袭置,发 中卡扣裝置包含有: ^ 兩個形成於基座頂面、且各設有—定位珠之定 - 與 , 兩形成於蓋體前端上、且分別對應兩定位珠之珠槽。 8 ·如申請專利範圍第7項之光電化學檢測裝置,其 中蓋體前端兩側各形成一肩槽,兩定位柱係分別對應於蓋_ 體的兩肩槽,並且兩珠槽係分別設於兩肩槽内。“、 9·如申請專利範圍第7或8項之光電化學檢測裝置 ’其中定位柱進一步包含有: 一形成於定位柱内部之螺孔; 一栓設於螺孔内之調節螺桿,調節螺桿軸 .t u战一軸 一容置於軸孔中頂持於所相對定位珠之彈性體,200526951 Scope of patent application: 1 · A photoelectrochemical detection method, which is mainly used in an electrochemical detection & electrode combined with photoelectrochemical materials, and generates photocurrent by illuminating to enhance the detection current in a detection liquid. To improve the accuracy and sensitivity of detection. — 2 · Photoelectrochemical detection method as described in item 1 of the scope of the patent application · 'where the electrode material is a copper alloy, which is selected from the group consisting of: · copper alloy, copper handle alloy, copper amalgam, copper Silver alloy and copper-gold alloy. 3 · The photoelectrochemical detection method described in item 1 of the scope of the patent application, wherein the electrode material is a derivative of copper, which is selected from the group consisting of: • gasified copper / smelted copper, arsenic copper, oxidized copper Copper, copper fluoride, copper hafnium and copper oxide. 4 · Photoelectrochemical detection method as described in item 2 of the scope of patent application ′ wherein the electrode material is a monovalent copper oxide. 5 · The photoelectrochemical detection method as described in item 2 of the scope of the patent application, wherein the electrode material is a divalent copper oxide. 6 · A photoelectrochemical detection device, the structure of which includes: a spring base, which has a top surface, a front end, and a rear end, and a receiving groove extending to the front end is formed on the top surface of the base; A cover body at the rear end of the base, the cover body has a top surface, a bottom surface rigid frame, a rear end and two sides, and the bottom surface of the cover body is formed with an elastic partition having an inner opening and corresponding to a receiving groove, and a light A hole and a plurality of flow holes are formed on the body k and communicate with the opening inside the separator; a detection electrode placed in the accommodation slot, the detection electrode corresponding to the light 16 200526951 is formed with tempeh / ^ Silke Research. X 'Bayou's semiconductor material with electrical conversion properties; and a snap device set between the base and the cover. 7. If the photoelectrochemical detection device of item 6 of the scope of patent application is applied, the buckle device in the hair contains: ^ two formed on the top surface of the base, and each provided with-positioning bead-and, two formed on The bead grooves on the front end of the cover body respectively correspond to two positioning beads. 8 · If the photoelectrochemical detection device of item 7 of the patent application scope, wherein a shoulder groove is formed on each side of the front end of the cover body, two positioning columns respectively correspond to the two shoulder grooves of the cover body, and the two bead grooves are respectively provided on the Inside the shoulder grooves. "、 9. If the photoelectrochemical detection device according to item 7 or 8 of the scope of application for patent, wherein the positioning post further includes: a screw hole formed inside the positioning post; an adjustment screw bolted in the screw hole to adjust the screw shaft .tu battle one shaft and one elastic body in the shaft hole to support the relative positioning beads, 藉由彈性體的彈力作用可將定位珠壓迫推 J 土禾槽,以 提供卡掣的效果。 1 0 ·如申請專利範圍第9項之光電化學檢測带置 其中該彈性體為一彈簧。 ^ 1 1 ·如申請專利範圍第6項之光電化學檢測裝置 其中蓋體底面形成有一環槽,環槽内容置有—i 具作為分隔 體之彈性墊圈,複數個流孔形成於蓋體上並分 J建通至臌 圈所圈住之範圍内。 17 200526951 1 2 ·如申請專利範圍第6項之光電化學檢測裝置, 其中光照孔係形成於蓋體頂面,蓋體之複數個流孔包含有 一形成與蓋體一側邊之第一流出孔; 一形成與蓋體同一側邊之第二流出孔;與 形成與蓋體另一側邊之注入孔<5 ' 1 3如申請專利範圍第6項之光電化學檢測裝置, ,.、中光妝孔係形成於蓋體頂面,蓋體之複數個流孔包含有 一形成與蓋體一側邊之第一流出孔; 一形成與蓋體同一側邊之第二流出孔;與 形成與蓋體另一側邊之注入孔。 ,1 4如申咐專利範圍第1 1項之光電化學檢測裝置 ^ 光…、孔係形成於盍體頂面,蓋體之複數個流孔包含 側邊之第_流出孔; 一側邊之第二流出孔;與 一側邊之注入孔。By the elastic force of the elastic body, the positioning beads can be pressed and pushed to the J soil groove to provide a locking effect. 10 · The photoelectrochemical detection belt according to item 9 of the application, wherein the elastic body is a spring. ^ 1 1 · If the photoelectrochemical detection device of item 6 of the patent application scope, a ring groove is formed on the bottom surface of the cover, and the ring groove is provided with -i an elastic gasket as a separator, and a plurality of flow holes are formed on the cover and Sub-J Jiantong to the area enclosed by the circle. 17 200526951 1 2 · The photoelectrochemical detection device according to item 6 of the patent application scope, wherein the illumination hole is formed on the top surface of the cover, and the plurality of flow holes in the cover include a first outflow hole formed on one side of the cover ; Forming a second outflow hole on the same side as the cover body; and forming an injection hole on the other side of the cover body < 5 '1 3 as in the photoelectrochemical detection device of the sixth scope of the patent application ,,,,, The light makeup holes are formed on the top surface of the cover, and the plurality of flow holes of the cover include a first outflow hole formed on one side of the cover body; a second outflow hole formed on the same side as the cover body; An injection hole on the other side of the cover. 14. If the photoelectrochemical detection device of item 11 of the patent scope is requested, light ..., holes are formed on the top surface of the carcass, and the plurality of flow holes in the cover body include the first outflow hole on the side; A second outflow hole; and an injection hole on one side. 一形成與蓋體一 一形成與蓋體同 一形成與蓋體另 項之光電化學檢測裝置 於第一流出孔。 項之光電化學檢測裝置 於第一流出孔。 項之光電化學檢測裝置 於弟二流出孔。 1 5 ·如申請專利範圍第1 3 其進一步包含有一參考電極連結 16 .如申請專利範圍第丄4 其進一步包含有-參考電極連結 1 7 ·如申請專利範圍第χ 2 其進—步包含有-輔助電極連結 18 200526951 1 8 ·如申請專利範圍第1 3項之光電化學檢測裝置 ,其進一步包含有一輔助電極連結於第二流出孔。 1 9 ·如申請專利範圍第1 4項之光電化學檢測裝置 ,其進一步包含有一輔助電極連結於第二流出孔。 2 0 ·如申請專利範圍第1 5項之光電化學檢測裝置 ,其進一步包含有一輔助電極連結於第二流出孔。 2 1 ·如申請專利範圍第2 0項之光電化學檢測裝置 ,其中容置槽為一鸠尾槽。 2 2 ·如申請專利範圍第2 1項之光電化學檢測裝置 ,其中於基座側邊各設有複數道止滑刻痕。 拾壹、圖式: 如次頁One photoelectrochemical detection device formed with the cover body and one formed with the cover body is formed in the first outflow hole. Xiang's photoelectrochemical detection device is in the first outflow hole. Xiang Zhi's photoelectrochemical detection device Yu Di's outflow hole. 1 5 · If the scope of the patent application is No. 1 3, it further includes a reference electrode connection 16. If the scope of the patent application is No. 4 it further includes-the reference electrode connection 1 7 · If the scope of the patent application is No. 2 and its further steps include- -Auxiliary electrode connection 18 200526951 1 8 · The photoelectrochemical detection device according to item 13 of the patent application scope, further comprising an auxiliary electrode connected to the second outflow hole. 19 · The photoelectrochemical detection device according to item 14 of the patent application scope, further comprising an auxiliary electrode connected to the second outflow hole. 20 · The photoelectrochemical detection device according to item 15 of the patent application scope, further comprising an auxiliary electrode connected to the second outflow hole. 2 1 · The photoelectrochemical detection device according to item 20 of the patent application scope, wherein the containing groove is a dovetail groove. 2 2 · The photoelectrochemical detection device according to item 21 of the patent application range, wherein a plurality of anti-slip nicks are provided on the side of the base. Pick up, schema: as the next page 1919
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TWI650535B (en) * 2018-06-15 2019-02-11 財團法人國家實驗硏究院 System and method for detecting illumination amount
CN113533470A (en) * 2021-07-15 2021-10-22 中国人民解放军陆军军医大学 Photoelectrochemical sensing device and method for analyzing m5C and m6A in RNA
CN114252481A (en) * 2020-09-24 2022-03-29 禅谱科技股份有限公司 Multi-channel potentiostat device
CN114354725A (en) * 2020-10-13 2022-04-15 华广生技股份有限公司 Physiological signal detection device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI650535B (en) * 2018-06-15 2019-02-11 財團法人國家實驗硏究院 System and method for detecting illumination amount
CN114252481A (en) * 2020-09-24 2022-03-29 禅谱科技股份有限公司 Multi-channel potentiostat device
CN114354725A (en) * 2020-10-13 2022-04-15 华广生技股份有限公司 Physiological signal detection device
CN113533470A (en) * 2021-07-15 2021-10-22 中国人民解放军陆军军医大学 Photoelectrochemical sensing device and method for analyzing m5C and m6A in RNA

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