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Chương Ii Dược Liệu Chứa Carbohydrat

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Chương Ii Dược Liệu Chứa Carbohydrat CHƯƠNG II DƯỢC LIỆU CHỨA CARBOHYDRAT Bộ môn Dược liệu ThS. Nguyễn Thị Ánh Nguyệt Email: [email protected] 1 Mục tiêu học tập Sau khi học chương “Dược liệu chứa carbohydrat” học viên phải biết được: 1. Phân loại các carbohydrat và cấu trúc hóa học của tinh bột, cellulose, gôm, chất nhầy, pectin và các ß-glucan, fructan. 2. Các phương pháp để nhận biết và đánh giá dược liệu chứa các thành phần nói trên. 3. Chú trọng một số dược liệu chứa carbohydrat: Cát căn, Sen, Ý dĩ, Bông, Gôm Arabic, Gôm adragant, Sâm bố chính, Thạch và Linh chi. 2 Đại cương về Carbohydrat 3 Carbohydrat – Glucid – Saccharid Đầu tiên, tên carbohydrat vì phần lớn đường có thể viết dưới dạng Cn(H2O)n Một số đường không thể viết dưới CT tổng quát trên Ví dụ: methylpentose CH3-(CHOH)4-CHO Vài chất không phải đường lại viết được dạng CTTQ . Ví dụ: acid lactic CH3-CHOH-COOH = C3(H2O)3 Đổi tên carbohydrat thành Glucid. 4 Carbohydrat – Glucid – Saccharid Khái niệm: carbohydrat hay glucid là những hợp chất hữu cơ gồm các monosaccarid, các dẫn chất, hoặc các sản phẩm ngưng tụ của chúng. CT tổng quát: (CH2O)n với n ≥ 3 Là sản phẩm chính của quá trình quang hợp (TV, tảo, VK) Ở ĐV, tồn tại dưới dạng đường huyết & glycogen (gan, cơ). Chiếm ưu thế so với các HC hữu cơ khác trong tự nhiên. Tính trên trọng lượng khô (DW): • Thực vật 80 – 90% • Động vật < 2% 5 Carbohydrat • Các nguyên tố cấu tạo nên carbohydrat: glucos e (CH2O)n n Glucose / sugar Simple carbohydrates (sugars) Sucrose Starch complex carbohydrate 6 Carbohydrat – Phân loại 1. Monosaccharid : là đường đơn như glucose, galactose, fructose. 2. Oligosaccharid: có từ 2 đến 9 đường đơn. Disaccharide: chứa 2 đơn vị monosaccharide như sucrose, maltose, lactose – đường đôi. 3. Polysaccharid: gồm nhiều monosaccharid nối với nhau (> 10 đường đơn) Homopolysaccharid: có 1 loại đường duy nhất (tinh bột, cellulose, inulin…) Heteropolysaccharid: có ≥ 2 loại đường đơn khác nhau (gôm, pectin, chất nhầy…) 7 Carbohydrat – Phân loại Analogues of nucleic Types of Carbohydrates acids: General: Aldose | Ketose | Pyranose | Furanose Triose | Tetrose | Pentose | Hexose | Heptose | Cyclohexane conformation | Geometry: Anomer | Mutarotation Glyceraldehyde | Dihydroxyacetone | Erythrose | Threose | Erythrulose | Small/Large: Sedoheptulose Trioses: Ketotriose (Dihydroxyacetone) | Aldotriose (Glyceraldehyde) Tetroses: Erythrulose | Erythrose | Threose Pentoses: Arabinose | Deoxyribose | Lyxose | Ribose | Ribulose | Xylose | Xylulose Glucose | Galactose | Mannose | Gulose | Idose | Talose | Allose | Altrose | Hexoses: Fructose | Sorbose | Tagatose | Psicose | Fucose | Rhamnose Disaccharides: Sucrose | Lactose | Trehalose | Maltose Glycogen | Starch (Amylose | Amylopectin) | Cellulose | Chitin | Stachyose | Polymers: Inulin | Dextrin Heparin | Chondroitin sulfate | Glucosamin | Hyaluronan | Heparan sulfate Glycosaminoglycans: | Dermatan sulfate | Keratan sulfate Kanamycin | Streptomycin | Tobramycin | Neomycin | Paromomycin | Aminoglycosides: Apramycin | Gentamicin | Netilmicin | Amikacin 8 1 – Monosaccharid Định nghĩa: là những polyhydroxyaldehyd (aldose) và polyhydroxyceton (cetose) có ≥ 3 carbon. Aldose (Vd: glucose) Ketose (Vd: fructose) chứa nhóm keto, thường ở C2. chứa nhóm aldehyd H O CH2OH O H OH HO H HO H H OH H OH H OH H OH CH2OH CH2OH D-glucose D-fructose (aldohexose) (ketohexose) Tồn tại dưới dạng mạch hở hoặc mạch vòng (bán acetal) Sản phẩm ngưng tụ là oligosaccharid và polysaccharid 9 1 – Monosaccharid Sự hình thành vòng furan và pyran 10 1 – Monosaccharid (tt) Tùy thuộc vào cấu tạo của cầu nối (1 4 hay 1 5), vòng có thể ở dạng 5 cạnh hay 6 cạnh (furanose hay pyranose). Việc đóng vòng đưa đến 2 đồng phân bán acetal, và gọi là đồng phân anomer. Cấu hình là khi nhóm OH bán acetal (C1) có cùng hướng với nhóm CH2OH thứ cấp đã được xác định trong chuỗi. Trường hợp ngược lại sẽ là cấu hình 11 1 – Monosaccharid (tt) • Cấu hình: Đồng phân lập thể dạng D và L Nhóm OH CHO CHO (ở C* xa nhất) H C OH HO C H CH2OH CH2OH • Bên phải: cấu hình D D-GLYCERALDEHYDE L-GLYCERALDEHYDE • Bên trái: cấu hình L CHO CHO H C OH HO C H Monosaccharid cấu hình D CH2OH CH2OH chiếm đa số trong tự nhiên. D-GLYCERALDEHYDE L-GLYCERALDEHYDE 12 1 – Monosaccharid (tt) ALDOTRIOSE 1 CHO Cấu hình các D-Aldose theo 2 H OH 3 CH2OH Fisher D-Glyceraldehyde ALDOTETROSES 1 CHO CHO 2 H OH HO H 3 H OH H OH 4 CH OH 2 CH2OH D-Erythrose D-Threose ALDOPENTOSES 1 CHO CHO CHO CHO H OH HO H H OH HO H 2 H OH H OH HO H HO H 3 H OH H OH H OH H OH 4 CH OH CH OH 5 CH2OH 2 2 CH2OH D-Ribose (Rb) D-Arabinose (Ara) D-Xylose (Xyl) D-Lyxose (Lyx) ALDOHEXOSES 1 CHO CHO CHO CHO CHO CHO CHO CHO H OH 2 H OH HO H H OH HO H H OH HO H HO H H OH HO H HO H 3 H OH HO H HO H H OH H OH HO H HO H 4 H OH H OH H OH H OH HO H HO H 5 H OH H OH H OH H OH H OH H OH H OH H OH CH OH CH OH CH OH CH OH CH OH CH OH 6 2 CH2OH 2 2 CH2OH 2 2 2 D-Allose D-Altrose D-Glucose D-Mannose D-Gulose D-Idose D-Galactose D-Talose 13 1 – Monosaccharid (tt) KETOTRIOSE 1 CH2OH 2 O 3 CH2OH Dihydroacetone KETOTETROSE 1 CH2OH 2 O Cấu hình các D-Ketose theo 3 H OH Fisher 4 CH2OH D- D-Erythurose Erythrulose KETOPENTOSES CH OH 1 CH2OH 2 O O 2 H OH HO H 3 H OH H OH 4 CH OH 5 CH2OH 2 D-Ribulose D-Xylulose KETOHEXOSES 1 CH OH CH OH CH OH 2 2 CH2OH 2 O 2 O O O H OH HO H HO H 3 H OH HO H 4 H OH H OH HO H H OH 5 H OH H OH H OH CH OH CH OH CH OH 6 2 2 CH2OH 2 D-Psicose D-Fructose D-Sorbose D-Tagatose 14 1 – Monosaccharid (tt) CÁC ĐƯỜNG THƯỜNG GẶP 1 CHO CHO CH2OH CHO 2 H C H C OH C=O OH H C OH 3 HO C H HO C H HO C OH HO C H 4 H C OH HO C H H C OH HO C H 5 H C OH H C OH CH OH CH2OH 2 CH2OH 6 CH2OH L-Arabinose D-Galactose D-Xylose D-Fructose 15 1 – Monosaccharid (tt) CẤU HÌNH LẬP THỂ Vì các carbon trong vòng thuộc loại sp3 nên những phân tử sau không nằm trong mặt phẳng mà có biến đổi: dạng ghế, dạng thuyền, dạng nửa ghế ... OH HO OH OH HO o O HO OH OH OH OH Cấu hình lập thể của -D-Glucopyranose 16 1 – Monosaccharid (tt) Tính chất vật lý: Tan trong nước, không tan trong dung môi hữu cơ. Không màu, có vị ngọt. Không bay hơi. Có tính quang hoạt: làm lệch mặt phẳng của ánh sáng phân cực khi cho ánh sáng đi quang dung dịch đường. 17 2 – Oligosaccharid “Oligo-” theo tiếng Hy lạp có nghĩa là một ít (few) “mono-” = một “poly-” = nhiều (vd: polysaccharid, polyphenol) “Holo-” = toàn thể (vd: holopolysaccharid, holosid) “Hetero-” = khác nhau (vd: heteropolysaccharid, heterosid) Oligosaccharid tan tốt trong nước, có vị ngọt. Cấu tạo: mạch thẳng hay phân nhánh. Bị thủy phân trong môi trường acid hoặc enzyme để tạo thành đường đơn, khá bền trong môi trường kiềm. 18 2 – Oligosaccharid Một số oligosaccharid thường gặp: Maltose (glucose-α-1,4-glucose) Sucrose (glucose-α-1,2-frutose) Lactose (galactose-α-1,4-glucose) Cellobiose (glucose-ß-1,4-glucose) 19 Raffinose (α-D-galactopyranosyl-(1-6) α-D-glucopyranosyl-(1-2) ß-D-fructosefuranosid) 3 – Polysaccharid (Tinh bột, cellulose, gôm, chất nhầy, pectin…) TINH BỘT Định nghĩa: là sản phẩm từ quang tổng hợp của cây xanh dự trữ trong hạt, củ, rễ, quả, thân (2-70%), trong lá (≤ 1-2%). Tinh bột tồn tại dưới dạng hạt có hình dạng và kích thước khác nhau. Không tan trong nước lạnh. Đun với nước bị “hồ hóa” và độ nhớt tăng lên. Trong cây dưới tác động của enzyme, tinh bột bị cắt 20 thành đường hòa tan để đến các bộ phận của cây..
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