فهرست:
چکیده .........................................................................................................................................................................
فصل اول:فوران و چگونگی تولیدآن در غذا و سرطان زایی اش....................................................................................1
1-1 فوران چیست؟...................................................................................................................................................................2
1-2 شکل گیری فوران در غذا..................................................................................................................................................2
1-2-1 غذای کودک حاوی ویتامینC.......................................................................................................................................4
1-2-2 معتبر سازی روش اندازه گیری......................................................................................................................................4
1-3 ارزیابی سیستم مدل ...........................................................................................................................................................5
1-4 اثر عوامل داخلی و خارجی ...............................................................................................................................................5
1-4-1 اثر نوع بافر و PH .........................................................................................................................................................6
1-4-2 اثر غلظت اسید آسکوربیک ...........................................................................................................................................6
1-4-3 اثر نسبت مولار اسید آسکوربیک به دهیدروآسکوربیک اسید.........................................................................................6
1-4-4 اثر حضور پروتئین .......................................................................................................................................................7
1-4-5 اثر زمان و درجه حرارت گرما دادن تشکیل فوران ........................................................................................................7
1-4-6 اثر سایر ترکیبات روی تشکیل فوران ............................................................................................................................7
1-5 فرآیندUV .........................................................................................................................................................................8
1-6 اثر بر سلامت .....................................................................................................................................................................9
1-7 متابولیسم .........................................................................................................................................................................10
1-8 استراتژی های تکنولوژیکی به منظور کاهش فوران .........................................................................................................11
1-9 استراتژیکی پیشگیری .......................................................................................................................................................12
1-9-1 تغییر در پارامتر های فرآیند .........................................................................................................................................12
1-9-2 تغییر در فرمولاسیون ...................................................................................................................................................13
1-9-3 حذف یا جایگزینی اجزا .............................................................................................................................................13
1-9-4 افزودن ترکیبات ...........................................................................................................................................................13
1-10 استراتژی های پس از فراوری........................................................................................................................................13
1-10-1 استراتژی های حذف ................................................................................................................................................14
1-10-2 پختن در ظروف در باز .............................................................................................................................................14
1-10-3 حذف فیزیکی ...........................................................................................................................................................14
1-10-4اشعه یونیزه کننده .......................................................................................................................................................15
1-11 گزینه های کنترل............................................................................................................................................................15
1-12 قانون گذاری..................................................................................................................................................................16
1-13 مروری بر تحقیقات گذشته ..........................................................................................................................................16
فصل دوم :ریز استخراج فاز جامد با استفاده از جاذب پلیمری قالب مولکولی ....................................................... .19
مقدمه ................................................................................................................................................................................... 20
2-1 استخراج .................................................................................................................................................................. 20
2-1-1 خصوصیات حلال .................................................................................................................................................. 21
2-2 استخراج با حلال ........................................................................................................................................................ 22
2-3 استخراج با فاز جامد(SPE) ...................................................................................................................................... 22
2-4 ریز استخراج با فاز جامد(SPME) ........................................................................................................................... 23
2-4-1 مزایای میکرو استخراج با فاز جامد ....................................................................................................................... 24
2-4-2 پارامترهای بهینه سازی کردن میکرو استخراج با فاز جامد .................................................................................... 25
2-4-3 عوامل موثر بر مقدار ماده ی جذب شده ............................................................................................................... 26
2-4-4 انواع روش های نمونه برداری ............................................................................................................................... 26
2-4-5 انتخاب روش استخراج .......................................................................................................................................... 27
2-4-6 معایب میکرو استخراج با فاز جامد ......................................................................................................................... 27
2-4-7 انواع فایبرها ........................................................................................................................................................... 27
2-4-8 انواع روش های هم زدن در میکرو استخراج با فاز جامد ...................................................................................... 29
2-4-9 عوامل موثر بر میکرو استخراج با فاز جامد .......................................................................................................... 30
2-4-10 کاربردهای میکرو استخراج با فاز جامد ............................................................................................................. 30
2-5 سرنگ SPME ....................................................................................................................................................... 31
2-6 مروری بر تحقیقات گذشته SPME ........................................................................................................................ 32
2-7 انواع فازهای جامد ..................................................................................................................................................... 34
2-7-1 کربن(گرافیت) ....................................................................................................................................................... 35
2-7-2 سیلیکاژل ............................................................................................................................................................... 35
2-7-3 جاذب پلیمری ....................................................................................................................................................... 36
2-8 آشنایی با پلیمر و پایمریزاسیون ............................................................................................................................... 36
2-8-1 پلیمر چیست؟ ...................................................................................................................................................... 36
2-8-2 انواع پلیمر ساختاری .............................................................................................................................................. 36
2-8-3 بسپارها از نظر اثر پذیری در برابر حرارت به دو دسته تقسیم می شوند ................................................................. 36
2-8-4 انواع پلیمرها بر اساس منبع تهیه ............................................................................................................................ 37
2-8-5 انواع روش های پلیمریزاسیون ............................................................................................................................... 37
2-8-5-1 پلیمریزاسیون افزایشی ......................................................................................................................................... 37
2-8-5-2 پلیمریزاسیون تراکمی ........................................................................................................................................ 37
2-9 پلیمرهای قالب مولکولی ............................................................................................................................................ 37
2-9-1 مزایای پلیمرهای قالب مولکولی ............................................................................................................................... 39
2-9-2 عوامل سازنده یک پلیمر قالب مولکولی ................................................................................................................ 39
2-9-2-1 مونومر عاملی .................................................................................................................................................... 41
2-9-2-2 مولکول هدف(قالب) ......................................................................................................................................... 43
2-9-2-3 عامل اتصال عرضی .......................................................................................................................................... 43
2-9-2-4 حلال ................................................................................................................................................................ 44
2-9-2-5 آغازگر .............................................................................................................................................................. 45
2-9-3 انواع پلیمرهای قالب مولکولی .............................................................................................................................. 46
2-10 پلیمر قالب مولکولی کووالانسی ............................................................................................................................... 46
2-10-1 مزایای پلیمرهای قالب مولکولی کووالانسی ........................................................................................................ 47
2-10-2 معایب پلیمرهای قالب مولکولی کووالانسی ....................................................................................................... 47
2-11 پلیمرهای قالب مولکولی نیمه کووالانسی ............................................................................................................... 47
2-12 پلیمرهای قالب مولکولی غیر کووالانسی ............................................................................................................... 48
2-12-1 مراحل سنتز پلیمر قالب مولکولی ..................................................................................................................... 48
2-12-2 دلایلی که از روش غیر کووالانسی بیشتر استفاده می شود ................................................................................. 48
2-13 روش های تهیه پلیمر قالب مولکولی ....................................................................................................................... 48
2-13-1 پلیمریزاسیون توده ای .......................................................................................................................................... 49
2-13-2 روش پلیمریزاسیون رسوبی ................................................................................................................................ 49
2-13-3 پلیمریزاسیون با تورم چند مرحله ای ................................................................................................................... 49
2-13-4 پلیمریزاسیون سوسپانسیون .................................................................................................................................. 50
2-13-5 روش پیوند زنی ................................................................................................................................................... 50
2-14 کاربرد پلیمرهای قالب مولکولی ............................................................................................................................... 50
2-14-1 کاربرد پلیمرهای قالب مولکولی برای ریز استخراج با فاز جامد (SPME) ...................................................... 50
2-15-1 کاربرد پلیمرهای قالب مولکولی در حسگرها ...................................................................................................... 51
2-15-2 کاربرد پلیمرهای قالب مولکولی در غشاء ............................................................................................................ 51
2-15-3 کاربرد پلیمرهای قالب مولکولی در کاتالیزگرها ................................................................................................... 52
2-15-4 کاربرد پلیمرهای قالب مولکولی در کروماتوگرافی .............................................................................................. 52
فصل سوم : مطالعات تجربی .............................................................................................................................. 53
3-1 مواد مصرفی ............................................................................................................................................................... 54
3-2 دستگاه وری ............................................................................................................................................................... 54
3-2-1 التراسونیک ........................................................................................................................................................... 54
3-2-2 pH متر ................................................................................................................................................................ 54
3-2-3 بن ماری ............................................................................................................................................................... 54
3-2-4 کروماتوگرافی گازی GC ...................................................................................................................................... 54
3-2-5 آون ....................................................................................................................................................................... 55
3-2-6 همزن مغناطیسی(هیتر) ......................................................................................................................................... 55
3-2-7 سرنگ SPME .................................................................................................................................................... 55
3-2-8 دستگاه (IR) ....................................................................................................................................................... 56
3-3 تهیه پلیمر قالب مولکولی ........................................................................................................................................... 56
3-3-1 انتخاب عوامل ........................................................................................................................................................ 56
3-3-1-1 آنالیت یا نمونه ................................................................................................................................................. 56
3-3-1-2 مونومر عاملی مناسب ....................................................................................................................................... 56
3-3-1-3 عامل اتصال دهنده عرضی ............................................................................................................................... 57
3-3-1-4 حلال مناسب ..................................................................................................................................................... 58
3-3-1-5 آغازگر ............................................................................................................................................................ 58
3-3-2 روش سنتز پلیمر قالب مولکولی ............................................................................................................................ 59
3-4 بهینه سازی شرایط جذب فوران در روش ریز استخراج با پلیمر قالب مولکولی ......................................................... 60
3-4-1 تعیین ماکزیمم طول موج جذب ............................................................................................................................ 60
3-4-2 بررسی اثر نمک .................................................................................................................................................... 60
3-4-3 بررسی اثر زمان ................................................................................................................................................... 61
3-4-4 تاثیر pH محلول بر جذب پلیمر ....................................................................................................................... 62
3-4-5 تاثیر دما بر جذب پلیمر ....................................................................................................................................... 63
3-4-6 شناسایی فوران توسط دستگاه GC ....................................................................................................................... 63
3-4-6-1 برنامه دمایی دستگاه GC برای فوران ها ......................................................................................................... 63
فصل چهارم : بحث و نتیجه گیری ........................................................................................................................ 65
4-1 سنتز پلیمر قالب مولکولی و پلیمر شاهد ................................................................................................................... 66
4-1-1 پلیمریزاسیون پلیمر قالب مولکولی ....................................................................................................................... 66
4-1-2 مکانیسم سنتز پلیمر قالب مولکولی .........................................................................................................................68
4-1-3 طیف های FT-IR از پلیمر MIP و NIP .............................................................................................................68
4-2 بهینه سازی شرایط جذب فوران توسط پلیمر قالب مولکولی ..................................................................................... 70
4-2-1 اثر نمک بر جذب فوران ........................................................................................................................................ 70
4-2-2 اثر زمان بر جذب فوران ........................................................................................................................................ 71
4-2-3 اثر دما بر جذب فوران ........................................................................................................................................... 72
4-2-4 اثر pH محلول بر جذب پلیمر ............................................................................................................................... 73
4-2-5 شناسایی فوران توسط دستگاه GC ........................................................................................................................ 74
خلاصه ................................................................................................................................................................................. 75
پیوست................................................................................................................................................................................ 76
پیوست 1؛ طیف FT-IR از NIP، در محدوده 400-4000 cm-1 به روش قرص KBr ............................................... 76
پیوست 2؛ طیف FT-IR از MIP، در محدوده 400-4000 cm-1 به روش قرص KBr ............................................... 77
پیوست 3؛ طیف GC برای محلول 10 PPM فوران ........................................................................................................ 78
پیوست 4؛ طیف GC برای محلول 40 PPM فوران ........................................................................................................ 79
پیوست 5؛ طیف GC برای محلول 100 PPM فوران ....................................................................................................... 80
پیوست 6؛تصویر TEM از NIP،..........................................................................................................................................81
پیوست7؛تصویر TEMاز MIP،................................................................................................................................82
منابع ...................................................................................................................................................................................... 83
چکیده انگلیسی....................................................................................................................................................................... 88
منبع:
1: Ho, I-Pin; Yoo, Seong-Jae; Tefera, Sebhat(2005). Determination of Furan Levels in Coffee Using Automated Solid-Phase Microextraction and Gas Chromatography/Mass Spectrometry. Journal of AOAC International
2: Jeffry B. Plomley; Mila Lauševic and Raymond E. March.( 2000) Determination of dioxins/furans and PCBs by quadrupole ion-trap gas chromatography–mass spectrometry Mass Spectrometry Reviews
3: M.S. Altaki, F.J. Santos, M.T. Galceran(2007) Analysis of furan in foods by headspace solid-phase microextraction–gas chromatography–ion trap mass spectrometry. Journal of Chromatography A
4: Till Goldmann,*a Adrienne Périsset,a Francis Scanlana and Richard H. Stadlerb . (2005) Rapid determination of furan in heated foodstuffs by isotope dilution solid phase micro-extraction-gas chromatography – mass spectrometry (SPME-GC-MS). Analyst
5: E.E Renniea,C.A.F Johnsona, J.E Parkera, D.M.P Hollandb, (1998). A study of the spectroscopic and thermodynamic properties of furan by means of photoabsorption, photoelectron and photoion spectroscopy. Chemical Physics
6: Federica Bianchi, Maria Careri, Alessandro Mangia, Marilena Musci ,( 2005). Development and validation of a solid phase micro-extraction–gas chromatography–mass spectrometry method for the determination of furan in baby-food. Journal of Chromatography A
7: Nyman, Patricia J; Morehouse, Kim M; McNeal, Timothy P; Perfetti, Gracia A; Diachenko, Gregory W(2006). Single-Laboratory Validation of a Method for the Determination of Furan in Foods by Using Static Headspace Sampling and Gas Chromatography/Mass Spectrometry. Journal of AOAC International
8: Marika Jestoia Talvikki Järvinen, Eila Järvenpääb, Heli Tapanainenc, Suvi Virtanenc Kimmo Peltonena,( 2009). Furan in the baby-food samples purchased from the Finnish markets – Determination with SPME–GC–MS. Food Chemistry
9: Shin-Hwa Tzinga,Wang-Hsien Dingb.( 2010). Determination of melamine and cyanuric acid in powdered milk using injection-port derivatization and gas chromatography–tandem mass spectrometry with furan chemical ionization. Journal of Chromatography A
10: M.S. Altaki, F.J. Santos, M.T. Galceran.(2009). Automated headspace solid-phase microextraction versus headspace for the analysis of furan in foods by gas chromatography–mass spectrometry. Talanta
11: Begoña Fabrellasa, Paloma Sanza , Esteban Abadb , Josep Riverab, David Larrazábala.(2004) Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS. Chemosphere
12: J.A. van Rhijn, W.A. Traag , P.F. van de Spreng , L.G.M.Th. Tuinstra(1993). Simultaneous determination of planar chlorobiphenyls and polychlorinated dibenzo-p-dioxins and -furans in Dutch milk using isotope dilution and gas chromatography—high-resolution mass spectrometry. : Journal of Chromatography A
13: V. A. Yaylayan.(2006). Precursors, Formation and Determination of Furan in Food. Journal für Verbraucherschutz und Lebensmittelsicherheit
14: Kim M. Morehousea*, Patricia J. Nymana, Timothy P. McNeala, Michael J. DiNovia & Gracia A. Perfettia(2007). Survey of furan in heat processed foods by headspace gas chromatography/mass spectrometry and estimated adult exposure. Food Additives & Contaminants: Part A
15: Douglas G. Hayward ,*† Kim Hooper ,‡ and Denis Andrzejewski,(1998). Tandem-in-Time Mass Spectrometry Method for the Sub-Parts-per-Trillion Determination of 2,3,7,8-Chlorine-Substituted Dibenzo-p-dioxins and -furans in High-Fat Foods.Analytical chemistry
16: Marie-Louise Scippo, Gauthier Eppe, Edwin De Pauw, Guy Maghuin-Rogister(2004) DR-CALUX® screening of food samples: evaluation of the quantitative approach to measure dioxin, furans and dioxin-like PCBs. Talanta
17: S. Hasnipa*, C. Crewsa & L. Castlea(2007) Some factors affecting the formation of furan in heated foods. Food Additives & Contaminants
18: Becalski, Adam; Seaman, Stephen(2005). Furan Precursors in Food: A Model Study and Development of a Simple Headspace Method for Determination of Furan. Journal of AOAC International
19: C. Crews* and L. Castle(2007) A review of the occurrence, formation and analysis of furan in heat-processed foods. Trends in Food Science & Technology
20- Wang, H. Y., et al. (2006). "Syntheses of molecularly imprinted polymers and their molecular recognition study for benzotriazole." Reactive and Functional Polymers 66(10): 1081-1086.
21- Liu, Z., et al. (1999). "Experimental studies on affinity chromatography in an electric field." Journal of Chromatography A 852(1): 319-324.
22- Huse, K., et al. (2002). "Purification of antibodies by affinity chromatography." Journal of biochemical and biophysical methods 51(3): 217-231.
23- Stevenson, D. (1999). "Molecular imprinted polymers for solid-phase extraction." TrAC Trends in Analytical Chemistry 18(3): 154-158.
24- Alizadeh, T. (2010). "Preparation of molecularly imprinted polymer containing selective cavities for urea molecule and its application for urea extraction." Analytica Chimica Acta 669(1): 94-101.
25- Nicholls, I. A., et al. (2009). "Theoretical and computational strategies for rational molecularly imprinted polymer design." Biosensors and Bioelectronics 25(3): 543-552.
26- Turiel, E. and A. Martín-Esteban (2010). "Molecularly imprinted polymers for sample preparation: A review." Analytica Chimica Acta 668(2): 87-99.
27- Moreira, F., et al. (2012). "Host-Tailored Sensors for Leucomalachite Green Potentiometric Measurements." Journal of Chemistry 2013.
28- Balamurugan, K., et al. (2012). "Preparation and evaluation of molecularly imprinted polymer liquid chromatography column for the separation of Cathine enantiomers." Saudi Pharmaceutical Journal 20(1): 53-61.
29- Liu, W., et al. (2007). "A cloud point extraction approach using Triton X-100 for the separation and preconcentration of Sudan dyes in chilli powder." Analytica Chimica Acta 605(1): 41-45.
30- Mester, Z. and R. Sturgeon (2005). "Trace element speciation using solid phase microextraction." Spectrochimica Acta Part B: Atomic Spectroscopy 60(9): 1243-1269.
31-Guilherme Dias Rodrigues , Maria do Carmo Hespanhol da Silva , Luis Henrique Mendes da Silva, Fernanda Ju¨ rgensen Paggioli, Luis Antonio Minim, Jane Se´ lia dos Reis Coimbra Liquid–liquid extraction of metal ions without use of organic solvent, Separation and Purification Technology 62 (2008) 687–693.
32- Later, D. W., et al. (2008). "CUSTODION ™ SPME Syringe for Rapid Sample Collection and Sample Preparation of Drinking Water for the GC– MS Determination of Trihalomethanes
33- DeBruin, L. S., et al. (1998). "Solid-phase microextraction of monocyclic aromatic amines from biological fluids." Analytical chemistry 70(9): 1986-1992
34- Poon, K.-F., et al. (1999). "Determination of polynuclear aromatic hydrocarbons in human blood serum by proteolytic digestion—direct immersion SPME." Analytica chimica acta 396(2): 303-308
35- F. Sporkert FP. Use of headspace solid-phase microextraction(HS-SPME) in hair analysis for organic compounds. Forensic Science International107 2000:129–48.
36- Kataoka, H., et al. (2000). "Applications of solid-phase microextraction in food analysis." Journal of Chromatography A 880(1): 35-62
37- K.G. Furton, J.R. Almirall, M. Bi, J. Wang, L. Wu, J. Chromatogr. A 885 (2000) 419
38- Psillakis E, DM, Nicolas Kalogerakis. Monitoring the sonochemical degradation of phthalate esters in water using solid-phase microextraction. Chemosphere 54. 2004:849–57. Methamphetamine. Chromatographia. 2004:73:975–83.
39- Dj. Djozan, Y. Assadi, Chromatographia 60 (2004) 313
40- F.G. Tamayo ET, A. Mart´ın-Esteban, ∗. Molecularly imprinted polymers for solid-phase extraction and solid-phase microextraction: Recent developments and future trends. Journal of Chromatography A, 1152. 2007:32–40
41- Demeestere, K., et al. (2007). "Sample preparation for the analysis of volatile organic130-144 ):compounds in air and water matrices." Journal of Chromatography A 1153(1
42- Djozan D, TB. Preparation and evaluation of solid-phase microextraction fibers based on monolithic molecularly imprinted polymers for selective extraction of diacetylmorphine and analogous compounds. Journal of Chromatography A, 1166. 2007:16–23.
43- Aguinaga, N., et al. (2007). "Determination of 16 polycyclic aromatic hydrocarbons milk and related products using solid-phase microextraction coupled to gas chromatography–mass spectrometry." Analytica chimica acta 596(2): 285-290
44- Natalia Campillo RPn, Manuel Hern´ andez-C´ ordoba. Solid-phase microextraction combined with gas chromatography and atomic emission detection for the determination of cyclopentadienylmanganese tricarbonyl and methylcyclopentadienyl)manganese tricarbonyl in soils and seawaters. Journal of Chromatography A, 1173. 2007:139–45
.45- Ducki S, a, JM-G, a, AZe, a b, et al. Evaluation of solid-phase micro-extraction coupled to gas chromatography–mass spectrometry for the headspace analysis of volatile compounds in cocoa products. Talanta 74. 2008:1166–74.
46-Djozan, D. and B. Ebrahimi (2008). "Preparation of new solid phase micro extraction fiber on the basis of atrazine-molecular imprinted polymer: Application for GC and GC/MS screening of triazine herbicides in water, rice and onion." Analytica chimica acta 616(2): 152-159
47- Pecoraino, G., et al. (2008). "Distribution of volatile organic compounds in Sicilian groundwaters analysed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry (SPME/GC/MS)." Water research 42(14): 3563-3577
48- Djozan, D., et al. (2009). "Preparation and binding study of solid-phase microextraction fiber on the basis of ametryn-imprinted polymer: application to the selective extraction of persistent triazine herbicides in tap water, rice, maize and onion." Journal of Chromatography A 1216(12): 2211-2219
49- G.A. Zachariadisa b, ∗, ER. Determination of butyl- and phenyltin compounds in human urine by HS-SPME after derivatization with tetraethylborate and subsequent determination by capillary GC with microwave-induced plasma atomic emission and mass spectrometric detection. Talanta 78. 2009:570–6
50- Nicolle J, a b, VD, a, PM, b, et al. Optimization of FLEC®-SPME for field passive sampling of VOCs emitted from solid building materials. Talanta80. 2009:730–7
51- He, J., et al. (2010). "Preparation and evaluation of molecularly imprinted solid-phase micro-extraction fibers for selective extraction of phthalates in an aqueous sample." Analytica chimica acta 674(1): 53-58
52- Filho AM, a b, FNdS, a, PAdPP, a c, d,, et al. Development, validation and application of a method based on DI-SPME and GC–MS for determination of pesticides of different chemical groups in surface and groundwater samples. Microchemical Journal 96. 2010:139–45.
53- Qiu L, a, WL, a, MH, b, et al. Preparation and application of solid-phase microextraction fiber based on molecularly imprinted polymer for determination of anabolic steroids in complicated samples. Journal of Chromatography A,1217. 2010:7461–70.
54- Rebière L, a, ACC, a, LMS, a, et al. A robust method for quantification of volatile compounds within and between vintages using headspace-solid-phase micro-extraction coupled with GC–MS – Application on Semillon wines. Analytica Chimica Acta660. 2010:149–57.
55- Prasad BB, MPT, Rashmi Madhuri, Piyush Sindhu Sharma. Development of a highly sensitive and selective hyphenated technique(molecularly imprinted micro-solid phase extraction fiber–molecularly imprinted polymer fiber sensor) for ultratrace analysis of folic acid. Analytica Chimica Acta662. 2010:14–22.
56- Djozan, D., et al. (2011). "Synthesis and application of high selective monolithic fibers based on molecularly imprinted polymer for SPME of trace methamphetamine." Chromatographia 73(9-10): 975-983
57- Jia, F., et al. (2012). "Using disposable solid-phase microextraction (SPME) to determine the freely dissolved concentration of polybrominated diphenyl ethers (PBDEs) in sediments." Environmental Pollution 167: 34-40
58- Natalia Campillo PVa, Rosa Pen˜alver, Juan I. Cacho, Manuel Herna´ndez-Co´rdoba*. Solid-phase microextraction followed by gas chromatography for the speciation of organotin compounds in honey and wine samples: A comparison of atomic emission and mass spectrometry detectorss. Journal of Food Composition and Analysis 25 2012:66–73.
59- Mousa, A., et al. (2013). "Application of electro-enhanced solid-phase microextraction for determination of phthalate esters and bisphenol A in blood and seawater samples." Talanta