臺灣博碩士論文加值系統

本研究旨在利用電化學中簡單的電沉積技術製備得氧化金修飾網版印刷碳電極(AuOSPE)，並利用此電極偵測燙髮劑中亞硫酸離子(SO32-)含量，得到電催化訊號在+0.4 V(Ag/AgCl)。並且與市售蒸鍍金電極(AuSPE)做比對，結果在偵測同樣濃度100 mgL-1 SO32-下，AuOSPE能得到大於八倍的訊號，因此，再詳細探討電極表面的元素分析與物理特性，證實在製備AuOSPE時能有較多的氧原子存在(金:氧=1:1)，進而能提高偵測時的靈敏度。
　將AuOSPE結合電化學中的安培法並配合流動注入分析系統，對SO32-進行偵測，為達到電極對於SO32-偵測訊號的最大化，實驗中探討了工作電極之製備及影響FIA系統操作條件。實驗結果本電極在0.1M pH6之磷酸載送流體下，定量測得之線性範圍為0.05~1200 mgL-1(R=0.9987)，偵測極限可低至0.03 mgL-1(S/N=3)。另外，電極穩定性探討中SO32-濃度20、300及900 mgL-1則分別是3.30 %、2.30 %與4.26 % (n=10)，皆在要求範圍內(RSD＜5%)；真實樣品之回收率為96.18 %~105.61 %。而本研究所製備之AuOSPE，具備體積小、再現性佳以及較高靈敏度等優點，與網版印刷電極的結合，更使電極具有可拋棄式、成本低廉等優勢。本電極應用於偵測SO32-時，可使之偵測流程簡便化，並達到快速準確偵測的目的。

An electrodeposition oxygen-incorporated gold-modified screen-printed carbon electrode (AuOSPE) was fabricated to determine the sulfite content in hair waving products. The AuOSPE showed an electrocatalytic current for sulfite at +0.4 V (vs. Ag/AgCl). Compared with a gold screen-printed electrode (AuSPE), the AuOSPE showed higher electrocatalytic current. The increase in the electrocatalytic current was ascribed to the increase of the oxygen incorporated with gold atom on AuOSPE. The AuOSPE coupled with a flow injection analysis (FIA) system showed excellent oxidation current for sulfite in a 0.1 molL-1 phosphate buffer solution (PBS), pH 6. The linear working range for determining the sulfite content was 0.05 to 1200 mgL-1 (0.625 molL-1 to 15.00 mmolL-1) with a calculated detection limit of 0.03 mgL-1(0.375 mol L-1) (DL, S/N = 3). Relative standard deviations (RSD %) of 3.30 %, 2.30 % and 4.26 % were calculated for consecutive injections (n=10) of 20, 300 and 900 mgL-1 sulfite, respectively. The amount of sulfite in two hair waving products was determined by the proposed method and a standard iodometric method. The recoveries ranged from 96.18 % to 105.61 %. The AuOSPE showed high sensitivity, selectivity, stability and reproducibility for sulfite.

中文摘要　I
Abstract　III
目錄　IV
表目錄　VIII
圖目錄　IX
第1章　緒論　1
　1.1　前言　1
　1.2　頭髮結構之介紹　2
　1.3　燙髮劑　4
1.3.1　燙髮之作用機轉　4
1.3.2　燙髮劑-亞硫酸鈉之簡介　6
1.3.3　燙髮型式-熱燙　7　　
1.4　偵測亞硫酸鹽之文獻方法比較　8
　1.5　研究動機與目的　15
　1.6　電化學原理與方法　16
1.6.1　循環伏安法(Cyclic Voltammetry, CV)　16
1.6.2　電位安培法(Amperometry i-t Curve)結合流動注入分析法
　　　(Flow Injection Analysis, FIA)　17
第2章　實驗部分19
　2.1　儀器及電極裝置　19
　2.2　藥品　23
2.2.1　藥品種類　23
2.2.2　分析藥品與標準溶液配製方法　25
　2.3　研究架構　27
　2.4　電極製備部分　28
2.4.1　修飾電極需具備的特點　28
2.4.2　以金鍍液配合電鍍法製備氧化金修飾電極(AuOSPE)　28
　2.5實驗步驟與方法　29
2.5.1　AuOSPE之基本電化學測試　29
2.5.2　使用不同金鍍液濃度實驗　29
2.5.3　使用不同電鍍電位實驗　30
2.5.4　使用不同電鍍時間實驗　30
2.5.5　使用不同濃度硫酸實驗　31
2.5.6　AuOSPE表面型態分析　31
2.5.7　不同掃描速率實驗　32
2.5.8　 AuOSPE偵測之不同電位處理　32
2.5.9　 AuOSPE偵測之之不同流速處理　33
2.5.10　 AuOSPE偵測之不同pH值處理　33
2.5.11　 AuOSPE偵測之不同載體溶液離子強度處理　34
2.5.12　校正曲線實驗　34
2.5.13　再現性實驗　36
2.5.14　真實樣品回收率實驗　36
第3章　結果與討論　41
　3.1　AuOSPE的製備條件影響SO32-偵測之探討　41
3.1.1　不同金鍍液濃度之影響　41
3.1.2　不同電鍍電位之影響　43
3.1.3　不同電鍍時間之影響　45
3.1.4　以不同濃度硫酸電解質配製金鍍液之影響　47
　3.2 　AuOSPE偵測SO32-之電化學行為分析探討　49
3.2.1　AuOSPE與AuSPE偵測SO32-之訊號比較　50
3.2.2　氧對於SO32-偵測之影響　54
3.2.3　不同電極對SO32-偵測之電催化氧化反應　56
3.2.4　反應機制探討　58
　3.3　AuOSPE偵測SO32-時最佳條件探討　59
3.3.1　偵測SO32-時不同電位之探討　59
3.3.2　偵測SO32-時不同流速之探討　61
3.3.3　偵測SO32-之載體溶液pH之選擇　63
3.3.4　偵測SO32-之載送流體離子強度之選擇　65
3.3.5　偵測SO32-之進樣管路大小之選擇　67
　3.4　分析上之應用　69
3.4.1　偵測SO32-之校正曲線　71
3.4.2　不同金電極偵測SO32-之訊號比較　73
3.4.3　偵測SO32-之穩定性探討　74
3.4.4　偵測SO32-之干擾探討　75
3.4.5　真實樣品偵測與碘滴定法方法比對　77
第4章　結論　79
第5章　未來展望　80
第6章　參考文獻　81

Haisman DR, The effect of sulphur dioxide on oxidizing enzyme systems in plant　tissues. J Sci Food Agric. 25 (1974) 803-810.
Wedzicha BK, Lamikanra O, Herrera JC, Panahi, Chemistry of Sulphur Dioxide in Foods. Food Chem. 15 (1984) 141-155.
“SULFUR DIOXIDE AND SULFITES.”McWeeny DJ, J Sci Food Agric. 25 (1974) 735-746.
Official Journal of the European Community, Council Directive 95/2/EC, 20th February 1995.
“Toxic Food Preservatives: Sulphur Dioxide and Sulfites.”　http://www.fedupwithfoodadditives.info/factsheets/Factsulphites.html, accessed in January 2011.
H. Vally, A. Carr, J. El-Saleh, P. Thompson, Wine-induced asthma: a placebo-controlled assessment of its pathogenesis. J. Allergy Clin. Immun. 103 (1999) 41-46.
The scientific committee on cosmetic products and non-food products intended for consumers, Evaluation and opinion on : inorganic sulfites and bisulfites, adopted by the SCCNFP during the 23rd plenary meeting of 18 March 2003.
AOAC official method 962.16. In P. Cunnif (Ed.), Official methods of analysis of AOAC international (16th ed., Vol. II), 1995.
United States Environmental Protection Agency Method 337.1 http://www.epa.gov/region1/lab/qa/projectplantool/Mod4References/AnalyticalReferences/40cfr136_03.pdf Access at 13, 12, 2011.
O. Fatibello-Filho, I.C. Vieira, Flow-injection spectrophotometric determination of sulfite using a crude extract of sweet-potato root(Ipomoea-bataras(L.)LAM.) As a source of polyphenol oxidase. Anal. Chim. Acta 354 (1997) 51-57.
N. Sarlak, M. Anizadeh. Simultaneous kinetic spectrophotometric determination of sulfide and sulfite ions by using an optode and the partial least squares(PLS) regression. Sens. Actuat. B-Chem. 160 (2011) 644-649.
Y. Miura, M. Hatakeyama, T. Hocino and P.R. Haddad. Rapid ion chromatography of L-ascorbic acid, nitrite, sulfite, oxalate, iodide and thiosulfate by isocratic elution utilizing a postcolumn reaction with cerium (IV) and fluorescence detection. J. Chromatogr. A 956 (2002) 77-84.
M. Koch, R. Köppen, D. Siegel, A. Witt, I. Nehls. Determination of total sulfite in wine by ion chromatography after in-sample oxidation. J. Agr. Food Chem. 58 (2010) 9463-9467.
M. Iammarino, A. D. Taranto, M. Muscarella, D. Nardiello, C. Palermo, D. Centonze, Development of a new analytical method for the determination of sulfites in fresh meats and shrimps by ion-exchange chromatography with conductivity detection. Anal. Chim. Acta 672 (2010) 61-65.
E. R. Sartori, H. H. Takeda, O. Fatibello-Filho. Indirect determination of sulfite using a polyphenol oxidase biosensor based on a glassy carbon electrode modified with multi-walled carbon nanotubes and gold nanoparticles within a poly(allylamine hydrochloride) film. Electroanal. 23 (2011) 2526-2533.
P. Kalimuthu, J. Tkac, U. Kappler, J. J. Davis, P. V. Bernhardt, A highly sensitive electrochemical sulphite biosensor incorporating a bacterial sulphite dehydrogenase. Anal. Chem. 82 (2010) 7374-7379.
M. Situmorang, D. B. Hibbert, J. J. Gooding, D. Barnett, A sulfite biosensor fabricated using electrodeposited polytyramine: application to wine analysis. Analyst 124 (1999) 1775-1779.
M. R. Majidi, K. Asadpour-Zeynali, K. Shahmoradi, Y. Shivaeefar. Electrochemical Characteristics of a Copper Hexac ferrate(CuHCNF) Modified Composite Carbon Electrode and its Application toward Sulfite Oxidation. J. Chin. Chem. Soci. 57 (2010) 391-398.
C.Chinvongamorn, K. Pinwattana, N. Praphairaksit, T. Imato, O. Chailapakul, Amperometric Determination of Sulfite by Gas Diffusion-Sequential Injection with Boron-Doped Diamond Electrode. Sensors 8 (2008) 1846-1857.
M. Scampicchio, N.S. Lawrence, A. Arecchi, S. Mannino. Determination of Sulfite in Wine by Linear Sweep Voltammetry. Electroanal. 20 (2008) 444-447.
O. Ordeig, C. E. Banks, F. J. del Campo, F. X. Muñoz, J. Davis, R. G. Compton. Sulfite Determination at In Situ Plated Copper Modified Gold Ultramicroelectrode Arrays. Electroanal.18 (2006) 247-252.
S.S. Kumar, S. S. Narayanan. Electrocatalytic Oxidation of Sulfite on a Nickel Aquapentacyanoferrate Modified Electrode:Application for Simple and Selective Determination. Electroanal. 20 (2008) 1427-1433.
A. Safavi, N. Maleki, S. Momeni, F. Tajabadi, Highly improved electrocatalytic behavior of sulfite at carbon ionic liquid electrode:Application to the analysis of some real samples. Anal. Chim. Acta 625 (2008) 8-12.
L.S.T. Alamo, T. Tangkuaram, S. Satienperakul, Determination of sulfite by pervaporation-flow injection with amperometric detection using copper hexacyanoferrate-carbon nanotube modified carbon paste electrode. Talanta 81 (2010) 1793-1799.
T. R. L. Dadmos, M. F. S. Teixeira, Electrochemical sensor for sulfite determination based on a nanostructured copper-salen film modified electrode. Electro. Chim. Acta 54 (2009) 4552-4558.
A. Siroueinejad, A. Abbaspour, M. Shamsipur, Electrocatalytic Oxidation and Determination of Sulfite with a Novel Copper-Cobalt Hexacyanoferrate Modified Carbon Paste Electrode. Electroanal. 21 (2009) 1387-1393.
R. Carballo, V. C. Dall’Orto, A. Lo Balbo, I. Rezzanol, Determination of sulfite by flow injection analysis using a poly[Ni-(protoporphyrin IX) chemically modified electrode. Sensor Actuat. B-Chem. B 88 (2003) 155-161.
H. Zhou, W.W Yang, C.Q.Sun, Amperometric sulfite sensor based on multiwalled carbon nanotubes/ferrocene-branched chitosan composites. Talanta 77 (2008) 366-371.
R. Rawal, S. Chawla, T. Dahiya, C. Pundir, Development of an amperometric sulfite biosensor based on a gold nanoparticles/ chitosan/ multiwalled carbon nanotubes/ polyaniline-modified gold electrode. Anal. Bioanal. Chem. 401 (2011)2599-2608.
P. Westbroek, J. De Strycker, K. Van Uytfanghe, E. Temmerman, Electrochemical behavior of sodium dithionite and sulfite at a gold electrode in alkaline solution. J. Electroanal. Chem 516 (2001) 83-88.
Y.V. Tolmachev, D.A. Scherson, The electrochemical oxidation of sulfite on gold:UV-Vis reflectance spectroscopy at a rotating disk electrode. Electrochim. Acta 49 (2004), 1315-1319.
R. Rawal, S. Chawla, C. S. Pundir, An electrochemical sulfite biosensor based on gold coated magnetic nanoparticles modified gold electrode. Biosens. Bioelectron. 31 (2012) 144-150 .
G. E. Casero, E. Lorenzo, F. Pariente, Electrochemical sensor for sulfite determination based on iron hexacyanoferrate film modified electrodes. Sens. Actuat. B-Chem. 106 (2005) 803-809.
A. J. Bard and L. R. Faulkner, ‘‘Electrochemical Methods; Fundamentals and Applications’’, John Wiley & Sons, New York (2001).
F. Scholz (Ed.), Electroanalytical Methods, Guide to Experiments and Applications, Springer, Berlin, (2002) ISBN 3-540-42229-3.
J. -M. Zen, A. Senthil Kumar, J.-C. Chen, Electrocatalylic Oxidation and Sensitive Detection of Cysteine on a Lead Ruthenate Pyrochlore Modified Electrode. Anal. Chem. 73 (2001) 1169-1175.
B. V. Crist,“Handbook of Monochromatic XPS Spectra, XPS International, LLC, USA”(2000).
K. Juodkazis, J. Juodkazyte, V. Jasulaitiene, A. Lukinskas, B. Sebeka, XPS studies on the gold oxide surface layer formation. Electrochem. Commun. 2 (2000) 503-507.