www.DaiHocThuDauMot.edu.vn B GIO DC V O TO VIN KHOA HC V CễNG NGH VIT NAM VIN HO HC Nguyn Quang Huy NGHIấN CU BIN TNH TINH BT BNG MT S TC NHN HểA HC V NG DNG LUN N TIN S HểA HC H Ni - Nm 2012 www.DaiHocThuDauMot.edu.vn B GIO DC V O TO VIN KHOA HC V CễNG NGH VIT NAM VIN HO HC Nguyn Quang Huy NGHIấN CU BIN TNH TINH BT BNG MT S TC NHN HểA HC V NG DNG Chuyờn ngnh: Mó s: Húa hu c 62.44.27.01 LUN N TIN S HểA HC NGI HNG DN KHOA HC: GS TS Nguyn Vn Khụi H Ni - Nm 2012 www.DaiHocThuDauMot.edu.vn i LI CAM OAN Tụi xin cam oan lun ỏn ny l cụng trỡnh nghiờn cu tụi v cỏc cng s thc hin Cỏc s liu, kt qu nờu lun ỏn l trung thc v cha tng c cụng b bt k cụng trỡnh no khỏc Tỏc gi Nguyn Quang Huy www.DaiHocThuDauMot.edu.vn ii LI CM N Trong thi gian thc hin cụng trỡnh nghiờn cu tụi ó nhn c nhiu s giỳp , úng gúp ý kin v ch bo chõn tỡnh ca Thy Cụ, bn bố, ng nghip v cỏc C quan Tụi xin by t lũng bit n sõu sc n Thy Giỏo s Tin s Nguyn Vn Khụi ó cho nhng kin thc vụ cựng quớ bỏu ng thi giỳp tn tỡnh cựng cỏc Anh Ch, bn bố, ng nghip Phũng Vt liu polyme luụn ng viờn, giỳp tụi thc hin thnh cụng lun ỏn tin s ny Tụi xin cm n chõn thnh Lónh o, phũng qun lý tng hp, cỏc bn ng nghip Vin Húa hc - Vin KH&CN Vit Nam ó ht lũng ng h giỳp tụi sut quỏ trỡnh thc hin lun ỏn ny Xin cm n cỏc bn ng nghip ti Vin Húa hc, cỏc n v phi hp nghiờn cu: Cụng ty dc phm H Thnh, Vin Húa Cụng nghip Vit Nam, Vin kim nghim thuc Trung ng, Tng cc tiờu chun o lng cht lng to mi iu kin thun li cng nh ng viờn, chia s tụi hon thnh nhng phn vic lun ỏn Cui cựng tụi xin chõn thnh cm n cỏc Thy cụ, Giỏo s, Phú giỏo s, Tin s ó úng gúp nhng ý kin quý bỏu giỳp tụi hon thin lun ỏn ny www.DaiHocThuDauMot.edu.vn iii DANH MC CC HIU V CH VIT TT AA : Axit acrylic AM : Acrylamit AN : Acrylonitrin AMS-1 : Tinh bt bin tớnh bng axit acrylic (Acrylic acid modified tapioca starch) AMS-2 : Tinh bt bin tớnh bng axit acrylamit (Acrylamit acid modified tapioca starch) Am : Amyloz Ap : Amylopectin AUL : hp th di ti trng (Absobency under load) BMA : n-butylmetacrylat CMS : Cacboxymetyl tinh bt DMSO : Dimetyl sulfoxyt DSC : Nhit vi sai quột (Differential Scanning Calorimetry) DTA : Phõn tớch nhit vi sai (Differential Thermal Analysis) DMF : Dimetyl formamit DS : th (Degree of subtitution) EPI : Epiclohydrin EMA : Etyl metacrylat FDA : C quan thc phm v thuc Hoa k (Food and Drug Administration) KPS : Kali persunfat KT : Keo t MBA : N,N'-metylenbisacrylamit MCA : Monoclo axetic axit MAM : Metacrylamit MAN : Metacrylonitrin www.DaiHocThuDauMot.edu.vn iv MA : Metyl acrylat MAA : Axit metacrylic PA : Copolyme RE : Hiu sut phn ng SEM : Kớnh hin vi in t quột (Scanning Electronic Microscopy) STMP : Matri trimetaphotphat SMCA : Natri monocloaxetat TGA : Phõn tớch nhit trng lng (Themal Gravimetric Analysis) TSTP : Trinatri trimetaphotphat TB : Tinh bt TB-G : Tinh bt ghộp XRD : Nhiu x tia X %GY : Hiu sut ghộp (Graft yield) %GE : Hiu qu ghộp ( Graft efficiency) %TC %KT : : Chuyn húa tng s (Total conversion) Phn trm keo t www.DaiHocThuDauMot.edu.vn v DANH MC CC BNG Trang Bng 1.1 Hm lng tinh bt mt s loi cõy Bng 1.2 Kớch thc ht amyloz c a mt s loi tinh bt Bng 1.3 Cỏc thnh phn tỏ dc cho thuc viờn 39 Bng 3.1 nh hng c a thi gian phn ng n quỏ trỡnh photphat hoỏ 75 Bng 3.2 nh hng c a nhit ti quỏ trỡnh photphat hoỏ 76 Bng 3.3 nh hng c a pH n quỏ trỡnh photphat hoỏ 77 Bng 3.4 nh hng c a t l mol photphat/glucoz n quỏ trỡnh photphat hoỏ 78 Bng 3.5 nh hng c a th ti bn lnh ụng - tan giỏ 83 Bng 3.6 nh hng c a t l axit/tinh bt n quỏ trỡnh thu phõn 92 Bng 3.7 nh hng c a nhit phn ng ti tc thu phõn 93 Bng 3.8 nh hng c a t l H2O/ tinh bt ti tc thu phõn 94 Bng 3.9 nh hng c a tỏc nhõn trung ho n nht v hm lng tro c a tinh bt bin tớnh 95 Bng 3.10 nh hng s ln n s thay i pH 96 Bng 3.11 nh hng lng nc n s thay i pH 96 Bng 3.12 Nhit h hoỏ (T0, Tp v Te) c a tinh bt t nhiờn v bin tớnh 101 Bng 3.13 Tớnh cht c a tinh bt bin tớnh bng axit 104 Bng 3.14 Mt s tớnh cht c a viờn nộn th nghim 104 Bng 3.15 S ph thuc c a trng lng phõn t trung bỡnh vo thi gian phn ng cỏc nhit khỏc 107 Bng 3.16 nh hng c a nhit phn ng n hiu sut thu hi sn www.DaiHocThuDauMot.edu.vn vi phm, hm lng cỏc nhúm chc cacbonyl, cacboxyl 108 Bng 3.17 S ph thuc c a trng lng phõn t trung bỡnh vo thi gian phn ng vi hm lng clo hot ng khỏc 110 Bng 3.18 nh hng c a hm lng clo hot ng n hiu sut thu hi sn phm, hm lng cỏc nhúm chc cacbonyl, cacboxyl 111 Bng 3.19 nh hng c a pH ti TLPT, hiu sut thu hi v hm lng cỏc nhúm chc cacboxyl, cacbonyl 112 Bng 3.20 nh hng c a nng tinh bt n quỏ trỡnh oxy hoỏ 113 Bng 3.21 Nhit h hoỏ (T0, Tp v Te) c a tinh bt t nhiờn v bin tớnh 117 Bng 3.22 Phõn tớch nhit trng lng c a tinh bt v tinh bt oxy hoỏ 119 Bng 3.23 nh hng c a cỏc vt liu h húa lờn cỏc tớnh cht c a si 121 Bng 3.24 nh hng c a thi gian polyme hoỏ lờn TC, GY, GE ghộp acrylic lờn tinh bt 123 Bng 3.25 nh hng c a nhit lờn TC%, GY%, GE% ghộp axit acrylic lờn tinh bt 124 Bng 3.26 nh hng c a nng axit acrylic lờn hiu sut ghộp v hiu qu ghộp 125 Bng 3.27 nh hng c a nng cht u lờn kh nng ghộp 126 Bng 3.28 nh hng c a t l lng/rn ti hiu sut ghộp 126 ng nh hng c a hm lng copolyme n quỏ trỡnh keo t 139 ng nh hng c a pH n quỏ trỡnh keo t 140 ng nh hng c a nng cht in ly ti quỏ trỡnh keo t 140 ng Hiu qu keo t c a copolyme vi copolyme ghộp 141 www.DaiHocThuDauMot.edu.vn vii DANH MC CC HèNH V V TH Trang Hỡnh 1.1 Cu trỳc phõn t amyloz Hỡnh 1.2 Cu trỳc phõn t amylopectin Hỡnh C ch thu phõn tinh bt bng axit 32 Hỡnh nh hng c a t l mol photphat/ glucoz ti hm lng tro 79 Hỡnh nh hng c a t l mol photphat/ glucoz ti tan c a tinh bt 80 Hỡnh nh hng c a th n kh nng trng c a tinh bt 80 Hỡnh nh hng c a t l mol photphat/glucoz n nht c a tinh bt 82 Hỡnh nh hng c a th n c a dung dch h tinh bt 84 Hỡnh nh SEM c a tinh bt cha bin tớnh 85 Hỡnh nh SEM c a TB photphat monoeste (t l mol photphat/glucoz 2,5:1) 85 Hỡnh Gin phõn tớch nhit trng lng c a tinh bt cha bin tớnh 87 Hỡnh Gin phõn tớch nhit trng lng c a tinh bt photphat hoỏ (t l mol photphat/glucoz 2,5:1) 87 Hỡnh 10 nh hng c a loi axit v thi gian n nht tinh bt sn bin tớnh 89 Hỡnh 11 nh hng c a loi axit v thi gian n hm lng tro c a tinh bt sn bin tớnh 91 Hỡnh 12 nh hng c a loi axit v thi gian n tan c a tinh bt sn bin tớnh 92 www.DaiHocThuDauMot.edu.vn viii Hỡnh nh hng c a nhit sy n nht sn phm 97 Hỡnh 14 nh hng c a thi gian sy n nht sn phm 98 Hỡnh 15 nh kớnh hin vi in t quột c a tinh bt sn t nhiờn (a) v bin tớnh vi t l lng axit/tinh bt ln lt l: 0,02 (b); 0,04 (c); 0,06 (d); 0,08 (e) v 0,10 (f) 99 Hỡnh 16 Gin phõn tớch nhit c a TB sn t nhiờn (1) v T bin tớnh vi t l axit/tinh bt ln lt l: 0,04 (2); 0,06 (3); 0,08 (4) v 0,10 (5) 100 Hỡnh 17 Gin nhiu x tia X c a tinh bt sn t nhiờn (1) v bin tớnh vi t l axit/tinh bt ln lt l: 0,02 (2); 0,06 ( ) v 0,10 (4) 102 Hỡnh 18 S phõn b kớch thc ht c a TB sn t nhiờn (A) v bin tớnh vi t l axit/tinh bt ln lt l: 0,02 ( ); 0,06 (C) v 0,10 (D) 103 Hỡnh S thay i lng clo tiờu th theo thi gian phn ng cỏc nhit khỏc 106 Hỡnh 20 nh hng c a hm lng clo hot ng ti lng clo tiờu th 108 Hỡnh 21 nh hng c a pH ti lng clo tiờu th 111 Hỡnh 22 nh SEM c a tinh bt sn (a,b) v tinh bt oxy hoỏ vi hm lng clo hot ng 1% (c,d), 2% (e,f) v 4% (g,h) 115 Hỡnh Gin nhiu x tia X c a tinh bt sn (1) v tinh bt oxy hoỏ vi t l clo hot ng so vi tinh bt l 1% (2), 2% ( ) v 4% (4) 115 Hỡnh 24 Gin DSC c a tinh bt v tinh bt oxy hoỏ 116 Hỡnh 25 Gin phõn tớch nhit c a tinh bt sn (T ) v tinh bt oxy hoỏ vi t l clo hot ng so vi tinh bt l 1% (T 1), 2% (T 2) v 4% (T 4) 118 www.DaiHocThuDauMot.edu.vn 150 A (2005), Carboxymethyl high amylose starch as excipient for Escherichia coli oral formulations, European Journal of Pharmaceutics and Biopharmaceutics, 60, p 53-60 [41] Huyghebaert N., Snoeck V., Vermeire A., Cox E., Goddeeris B M., emon J P (2005), Development of an enteric- coated pellet formulation of F4 fimbriae for oral vaccination of suckling piglets against enterotoxigenic Escherichia coli infections, European Journal of Pharmaceutics and Biopharmaceutics, 59, p 273-281 [42] Jutamas Tatongjai, Namfone Lumdubwong, (2010), 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DỤC VÀ ĐÀO TẠO VIỆN KHOA HỌC VÀ CÔNG NGHỆ VIỆT NAM VIỆN HOÁ HỌC Nguyễn Quang Huy NGHIÊN CỨU BIẾN TÍNH TINH BỘT BẰNG MỘT SỐ TÁC NHÂN HÓA HỌC VÀ ỨNG DỤNG Chuyên ngành: Mã số: Hóa hữu 62.44.27.01 LUẬN... tinh bột 1.2 Cấu trúc c a tinh bột 1.3 Một số tính chất c a tinh bột .1 Tính chất vật lý .2 Tính chất hóa học 1.4 Một số phương pháp biến tính tinh bột. .. tinh bột .20 1.4.3.5 Biến tính tinh bột axit .31 1.4 .6 Oxy hoá tinh bột .40 1.4.3.7 Biến tính tinh bột axit acrylic crylamit .48 1.5 Tình hình nghiên cứu biến tính tinh bột