Ứ Ƣ Ứ -KETO-L-GULONIC TRONG -2015 -2015 Ứ Ƣ Ứ -KETO-L-GULONIC TRONG uy t uy t v s ƣ 01.19 ƣ u GS.TSKH Mai Tuyên -2015 T ố , ố ố ố N , T L I CAM ƠN ủ Lyon é ĩ ỗ , Tôi xin ỗ quí KÝ Ữ Ắ (*) AAS Atomic Absorption Spectrophotometric - P ổ BET Brunauer Emmett Teller - Ph ơ DTA Differential Thermal Analysis - P EDX Energy Dispersive X-ray spectroscopy- P ổ HPA Acid 12- phosphotungstic (H3PW12O40) HPLC High Performance Liquid Chromatography - P ỏ IR Infrared Spectroscopy- P ổ KPW M ố Me-2KLG Methyl 2-keto-L-gulonat MeOH Me Methanol Methyl SBET D SEM Scanning Electron Microscopy - K SNDH Enzym Sorbosone Dehydrogenase TEM Transmission Electron Microscopy - K TGA Thermal Gravimetric Analysis - P TPD-NH3 Temperature Programmed Desorption NH3 XRD X-Ray Diffraction - P ổ XT/NL Xúc tác/ N ZS Zirconi sulfat hóa (SO42-/ZnO2) 13 Proton Nuclear Magnetic Resonance - P ổ 13 C C-NMR 2-KLGA - ắ X ắ ặ ễ ể ể ơng pháp ọ N X Acid 2-keto-L-gulonic “ ủ lu ” ý – phosphotungstic (KxH3-xPW12O40) (*) t ẳ & v t u t theo T ý Giá ị ằ 3.1 T T -KLGA ố o ú acid ắ ố ị eton ố T- ố 33 ú K Dữ ố ỷ T-C- sulf carbon sulf ú ú KxH3-xPW12O40 PA K2,25H0,75 ổ ion 50 K 3.8 D 39 Vị ú ố 68 ố ặ ú MxH3-xPW12O40 ú ổ ể K N ằ 92 B ng 3.11 Đ chuyển dịch hóa học c a nguyên t C K ị 92 + ổ 71 74 ọ 63 66 + 47 T-C- sulf 48 ú acid TPD-NH3 26 ặ ố 3.6 23 ể D 96 ể Anh 97 Hình 1.1 Hình 1.2 Hình 1.3 Sơ Sơ Dạ Hình 1.5 Hình 1.6 Hình 1.7 Hình 2.1 Hình 2.2 Dị Sơ Đ ọ acid ascorbic ố hai ổ vitamin C ổ -KL A L-sorbose   zirconi hydroxide ú K ( ) ú D w ( ) ú K ú H3PW12O40.6H2O ạ ể ù ễ Đ Hình 2.4 Các ẳ Sơ ị ố , , N, S, O P ổ DX ú T-C-sulf ể S M ú T-C-sulf P ổ IR TT-C-sulf Đ ể -KL A ú A BT-C-sulf T A DTA Z O(O )2 T M Z O(O )2 XRD ú ZS- ặ P ổ ú ZS- ặ S M ú ZS- ặ Gi TPD-NH3 c a xúc tác ZS- ặ ỷ XT NL ú ZS- ặ ể -KLGA Đ ể 2-KLGA xúc tác ZS, ZS- ặ Amberlyst-15 Đ ể -KL A ú ZS- ặ P ổ IR ZS- ặ tái Hình 3.2 3.3 3 3.7 3.8 Hình 3.9 Hình 3.10 Hình 3.11 3 Hình 3.14 3 ị ễ ở 3 ể P theo P/P0 W (P0  P) Hình 2.3 ổ ion ố ỏ ú tác Đ S M ẳ ú ọ ị ú 3PW12O40 N2-BET ú K2,25H0,75 K2,21H0,79, K2,25H0,75 K2,45H0,55 7 17 20 21 21 33 34 38 39 41 48 49 49 51 52 53 53 54 55 55 57 58 59 60 61 62 64 65 Hình 3.19 ú K2,25H0,75 Hình 3.20 TPD-NH3 úc tác HPA Hình 3.21 TPD-NH3 ú K2,25H0,75 Đ ể -KL A ú KPW PA 3 P ổ XRD ú PA, K2,25H0,75, Rb2,24H0,76 2,26H0,74 P ổ IR ú PA, K2,25H0,75, Rb2,24H0,76 Cs2,26H0,74 Hình 3.25 M ú K Hình 3.26 S M ú K2,25H0,75, Rb2,24H0,76 Cs2,26H0,74 Đ ể -KLGA ú K2,25H0,75; Rb2,24H0,76 2,26H0,74 Hình 3.28 ỷ ú ể 2-KLGA Hình 3.29 ỷ 2-KLGA /methanol ể 2-KLGA Hình 3.30 ể 2-KLGA Hình 3.31 ố ể 2-KLGA Hình 3.32 Đ ể -KL A ú , ú , ọ ỏ ú 33 ú K2,25H0,75 ba t ú 33 P ổ ú K2,25H0,75 ester -KLGA Hình 3.35 Sắ ý PL ẩ =7 Hình 3.36 Sắ ý PL n ố 3,3 ú Hình 3.37 Sắ ý PL M - KL 3, ú Hình 3.38 Sắ ý PL ẩ =9 Hình 3.39 Sắ ý PL ẩ = o Hình 3.40 Sắ ý PL ẩ C o Hình 3.41 Sắ ý PL ẩ 50 C o Hình 3.42 Sắ ý PL ẩ C Hình 3.43 ễ X ẩ Hình 3.44 P ổ ẩ 13 Hình 3.45 P ổ C-NMR ẩ natri ascorbat Hình 3.46 ễ X Hình 3.47 P ổ 13 Hình 3.48 Phổ C-NMR c a ascorbic 65 67 67 70 72 73 73 75 76 77 78 79 80 81 83 83 84 85 86 86 87 88 88 89 90 91 91 94 94 95 ……………… … … …………………………… C ƣơ ……………… ………………… … Sơ …………………………………………… 1.2 -keto -L…………………….… 1.2.1 M ố -keto-L……………… Q ổ acid 2-keto-L…………… P ester hóa ……………………………………………… Đặ ể ester…………………………… ester hóa…………………………… 33 ố ester ………… P ester ú ị ể… ……… …… Xú ị ể…………………………………………… Xú ………………………………… 1.4.2 Xú z (SO42-/ZrO2)… ……… … … Xú ị PA … … ……………… ƣơ Ự …………………………….… ……… Tổ ú ……………………………………… ……… Tổ ú ………… … …… Tổ ú zirconi ……… ……… … 2.2.3 Tổ ú ị ……………………… … …………………… ặ ú …………………… P (T A – DTA)……………… 2.2.2 Ph ễ X (XRD)… ………… …… 2.2.3 P ổ (IR)… ………… …… P ể (S M)… ……… …… P ể (T M)…………… P ổ ắ X ( DX)…… 2.2.7 Ph ẳ ( T) … P ổ (AAS)……… …… P ố , ,N,S,O…………… 2.2.9 P g N (TPD- NH3)……………………………………………………… 4 6 9 10 11 12 12 17 19 29 29 29 29 31 32 32 33 35 36 37 37 37 40 41 41 P NH3 2.3 uá trình ẩ ………… ………… 2.3.1 Q …………………………………… … Q …………………………… ……… 2.3.3 T ……………………………………… ẩ ………………………… P ắ ý ỏ ( PL )…… …… 13 P ổ C (13C-NMR) ƣơ K ………………………… 3.1 Xúc tác carbon …………………………………… 3.1.1 Đặ ý ú carbon … 3.1.2 H ú T- ester 2-KL A………………………………… 3.2 Xúc tác zirconi ……………………………… ……… 3.2.1 Đặ ý Z O(O )2…………… 3.2.2 Đặ ý ú zirconi sulfat hóa …… 3 ú SO42-/ZnO2…… …… … 3 Xú ị PA…………………………… … 3 Tổ ặ ú …………… 3.3.2 Nghiê ester -KL A methanol ú K2,25H0,75………………………………………………… N -keto-L-gulonat 3.4.1 …………… ……………… …………… 3 P ú ẩ T ẩ …… A ố T …………………… 3 Đ ẩ ……………… K ………………………………………………………… Ữ Ƣ Ứ ………… Ủ ………… K Ã Ố… K …………………… …………………… 10 43 44 44 44 45 45 45 46 47 47 47 50 51 51 53 56 60 60 77 84 84 88 90 92 92 93 93 98 100 101 102 104 K Đ ổ ú ặ , ), - , ẩ ẩ ( KL A ù 93,3%) ú , %) K A -15 ( ú ( ú -KL A Đ ổ ặ ú z V z N , , ặ ơ -KLGA ẩ 99,9%) K ol ( ú ẵ , ẹ N ố ể ổ ú ị ị ữ ù - -KL A ú K2,25H0,75PW12O40, ỏ ọ , ú, ố ò Đ ú K , ố ú ý AAS, BET, XRD, IR, TEM, SEM-EDX, TPD-NH3, T A-DTA, N ể ặ ổ ọ ữ ỷ o ổ -KL A XT NL = , o , ỷ ú K2,25H0,75PW12O40 -KLGA/methanol = 1/24 (mol/mol), , ố ò 98 ú Đ ị - - ể -Lo -L- , , + ổ ể ể ; , ẩ 99 = 9; o Ữ Ƣ Ứ N carbon sulfonat tác acid ị z ú r hóa nói ú ể 100 ú Ủ L ố ể ổ ú ị ú - acid K2,25H0,75PW12O40, ổ -L- Đ hóa acid 2-keto-L-gulonic ú ị ể, ặ ố ú K2,25H0,75PW12O40 ố , ố ữ S I ữ Đ V ằ N ổ ẩ ị Đ ố , , ẩ 101 ẩ K Vũ T ị T D ,P Q M T ,N ễ T ịT T ắ , ,( ú hóa acid 2-keto-L- Ã ị Ố M ,T Tọ , ) N ể SO42-/ZrO2 , 49(5AB), 276-279 Tâm, N ( ễ T ịT ) N “ gulonic P M ,P M T , Vũ T ị T ” -keto-L- , 50(5A), 297-300 M T , Vũ T ị T ,N , Vũ T ị T ễ T ịT ,( ụ ổ ò , Vũ T ị T Tọ ,( ,N ễ T ịT M ,P ị ụ ,N M ,N ễ T ịT ú T , , Đ Mạ ể ể ú T , – II ẩ Vũ T ị T M ) N Đ M ,P Tọ , , 3(13), 1-3 T M ,T ) N sorbitol – I Q ú , ọ , 4(14), 15-18 ,N ù ,( ễ T ịT ) V ò –I ắ , 7, 41-45 Thu Ha Vu Thi, Hang Thi Au, Tuyet Mai Thi Nguyen, Minh Tu Pham, Tam Thi Bach and Hong Nhan Nong, (2013) Esterification of 2-keto-Lgulonic acid catalyzed by a solid heteropoly acid Catalysis Science & Technology, 3, 699-705 ằ ữ - Vũ T ị T ,N Q ố T P ú -L- ễ T ịT ị Số M ,T 33 QĐ-S TT, 102 ị Tọ T ,P M T , Vũ T ị T ( , ) N 2-keto-L-gulonic ù N ọ Q ổ , N ú , ị – ụ 3, 20-25 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of Unsupported Dodecatungstophosphoric acid, and Its Cesium and potassium salts supported on silica Modern Research in Catalysis, 2, 110-118 111 K t qu K t qu p K t qu K t qu K t qu t -DTA [...]... ỏ -KL A ằ ester acid acid A x c t c l nh ạ acid ũ ằ ú acid ắ Tang [22 ] ổ trên x c t c Mặ ù ớ -KL A ớ methanol ester D ị , ú ố ị ổ ( ị ú ớ ể o ớ ị ạ ơ Xú ớ ) ạ siêu acid ị ú ể ạ , ổ ú ú 1.4 SIÊU ACID tá r su Trong ố t ú acid ị ể, ú ơ ở carbon sulfonat ố ữ acid acetic ớ ethanol, acid ữ ester ữ acid acetic ớ (acid palmitic, acid caprylic hay acid acid ) - (triaceti , ) ớ methanol X c t c trên ơ ở carbon... ơ ằ , M-O-M ú ơ ớ ị ú ạ D ò acid ằ ù Đ acid K ị N ú , ữ ị ò ị ất ủ acid [64] d đ acid acid ị acid- base ổ ữ ớ ù ) ẽ ữ ú 1.4.3.3 í bên ạ ị acid , ố ớ , ú ạ T acid, ể ị ễ ị ễ ằ ọ ị c tính acid ố ơ ú ữ acid acid ắ c c acid ị ố ạ acid ể acid ơ [60] ạ ơ ớ S O2-Al2O3, H3PO4/SiO2, zeolit HX và HY và 2SO4, HCl, acid p- ạ … ị ể ớ ớ , ặ ơ c c proton và anion 22 acid này ữ L ể acid acid Hammett Ho: Ho = pKBH+... ncol, ankyl hóa, M ester hóa, ạ acid ố ạ ơ ớ HCl, acid p-sulfonic toluen… Tuy nhiên HPA (< 15 m2 ) ặ ễ ị ò , Dị ớ ể ữ ý ặ ể ị ể ặ ú ị ể ù , ể cho ester ú ,z , ặ ạ -KLGA ớ , ị ơ D ú , ữ ú ố ặ ú ơ ú ạ -KL A ẽ ù ú ặ ạ acid ổ ơ ở ú - Tổ ổ n ẽ , - ố ạ ổ Để ị ể ữ , 2- keto- L- gulonic ị acid ắ S O2-Al2O3, H3PO4/SiO2, zeolit HX và HY và c c acid vô 2SO4, V c -phosphotungstic, H3PW12O40 ( PA) , acid l ể ú acid. .. tv t 1.1 ơ ủ -KLGA OH OH O ạ OH OH OH O K ố 194,14 Đặ ý M ắ ắ M Mùi Không mùi Để 159 C -1 62 C uá tr t p acid 2- keto- L- gulonic T ể ổ L- -KL A ạ HO OH men OH HO CH2OH L- sorbose L- sorbosone Q ếs tổ men t p -K H H OH HO H CH2OH ơ HO H H H 1 .2. 2.1 C O O H HO COOH CHO O H ơ Đ CH2OH HO ắ H CH2OH acid acid 2- keto- L- glulonic 2- keto- L- gulonic t -sorbose ợ 2- KLGA từ L- sorbose ổ -KL A L- ò Q ổ -KL A enzym sorbosone... ổ ị acid acid Ho= -11,94 D , ị 2SO4 o , ể acid ố 100% acid c giá ị %) ổ % ớ ị  B + H+ ẩ 2SO4 C c siêu acid ằ acid ơ ơ T ạ + ằ [ ạ, ể ]/[B] ị ;[ ; KBH+ Tỷ + ơ - o SO3F - SbF5 ạ acid [65] 8 ( ạ ị ố ớ acid H2SO4 ị ố acid ắ 1 .2 1 .2 o t t p STT ủ ts tx acid rắ ự acid Ho acid 1 H2SO4 -11,94 2 Nafion - 12, 0 3 H3PW12O40 -13 ,2 4 AlCl3 – CuCl2 -13,7 5 SbF5/SiO2 – Al2O3 -13,7 6 SO 42- /TiO2 -14,5 7 SO 42- /ZrO2 -16,1... ạ ơ ủ p ứ ơ c a ph n ng ester hóa dùng x c t c acid x y ra theo c c ester hóa ớ 9 : Acid carboxylic ẽ ú ẽ acid, ặ S ẽ ơ Đ acid carboxylic ơ carbon ị ở ặ ancol 3 T ớ 4: Proton ị ( á y ut L ạ ƣ ạ ẽ ú ) p ở ứ ester ằ ancol T , ancol - 0,67 mol ester ancol - 0,60 mol ester ancol - 0,05 mol ester ancol N , ố ạ ễ 3 ở ẩ N , ể ị ơ ố ẩ , ể , T ổ ester ạ ạ ằ ở ổ ạ ũ ổ, ằ ằ ổ T ể , ẩ ( ớ ester ớ ester ơ ể ằ ơ... (genetically modified organisms - GMOs) H % S ơ ổ , ữ Reichstein ơ, ố ễ ơ ơ ạ ễ , ố ạ , ạ ơ ơ , ặ ạ ởT Q ố ,N ạ L- 5 , Q ố ,Đ , ớ ( P ơ ): L D- L- sorbose thành 2- KLGA, ester hoá 2- KLGA ằ ặ ổ vòng (lacton hoá) và tr , ú , ể ố ù acid L- ascorbic ACID 2- KETO- L- GULONIC ts t P ơ ớ – OO , 2- KLGA –OH ( acid t ủ acid 2- keto- L- gulonic ) D ố , 2- KLGA ổ ạ h ạ =O ị , ỏ ị 6 base và ố, , ớ ạ ớ (x c t c H+),… ester và. .. ạ acid acetic (ở 3 3K), acid N z l ơ carbon ố ester ớ ở carbon Xú ố ú ẩ ớ ể ú ạ carbon, cho ở acid, trong khi ạ [25 ] carbon ớ acid sulfo 13 ằ ữ acid sulfuric ặ ớ carbon ẩ ú acid , ẹ tro ester ũ ố ú ớ ố acid ỏ ễ NT ) ạ ở3 ớ 2SO4 ú K % ( ơ 9 ằ ặ 3 ằ ớ ú NT ú 2SO4 ằ acid ắ H , ú M ù ú ạ [26 ] Xú carbon ẩ h sulfonat , D- ạ ú N ổ ú ớ carbon SA -13 hay H2SO4, ạ ơ ú acid ester hóa c c ( ) hay acid ( -ester... sulfonat hóa ể ạ ơ ớ ú ester hóa Xiao-Yan Liu [23 ] ố ố ọ ổ acid ị ổ ú z ữ ạ ú ester hóa acid ớ ặ N , ũ ớ c c x c t c acid ắ Nafion NR50 và Amberlyst- -benzene- acid H3PO2 l m t c nhân -SO3 2 ể ằ ạ Xú ớ A -SO3 ơ , ớ carbon ặ ể carbon sulfonat z ặ K ơ ạ ằ ,S ữ acid acetic ớ ancol ethylic, A -SO3 ( %) 12 ơ ớ ể ặ Amberlyst-15 ( %), ể ơ AC-SO3 ớ A ể nhiên, AC-SO3 ơ ớ ú ể ú ơ ớ , ể ạ ơ ơ ặ ạ ester hóa carbon... acid ( -ester hóa , ớ ) ớ methanol ỏ -ester ớ methanol, x c t c carbon hó ú , ơ (65 ò ớ T 3 Tố A -H2SO4 (20 mmol.min-1.g-1) ú ọ , ổ, X ớ ũ hay HNO3-CNTs (18 mmol.min-1.g-1) Mặ ạ ắ ữ methanol và acid acetic trong 1 mmol.min-1.g-1) ớ ể ớ hóm -SO3H c trong cetat ớ Đố ” ằ ị x c t c ạ ú ù acid ) S , carbon 3, ằ ạ K acid -SO3 ester , ẽ ạ N o ( ạ ể carbon ở ơ ể ơ ớ acid sulfuric trong chu trình 1 ạ ị TOF ... phộp carbon c c x c t c carbon acid , ỳ ỳ 3K acid acetic ( 3K), acid N z l carbon ester carbon Xỳ ỳ ỳ carbon, cho acid, [25 ] carbon acid sulfo 13 acid sulfuric carbon ỳ acid. .. sulfonat acid acetic ethanol, acid ester acid acetic (acid palmitic, acid caprylic hay acid acid ) - (triaceti , ) methanol X c t c trờn carbon sulfonat húa ỳ ester húa Xiao-Yan Liu... ũ acid ự acid K N ỳ , ũ t acid [64] d acid acid acid- base ự ) ỳ 1.4.3.3 bờn acid , , ỳ T acid, c tớnh acid ỳ acid acid c c acid acid acid [60] S O2-Al2O3,