Luận án Tiến sĩ Hóa học Nghiên cứu tổng hợp và đặc trưng vật liệu nanocomposit giữa hydroxyapatit và một số polyme tự nhiên

Header Page of 146 B GIO DC V O TO VIN HN LM KHOA HC V CễNG NGH VIT NAM VIN HểA HC NGUYN TH LAN HNG NGHIÊN CứU TổNG HợP Và ĐặC TRƯNG VậT LIệU NanoCOMPOSIT GIữA HYDROXYAPATIT Và MộT Số POLYME Tự NHIÊN Chuyờn ngnh: Húa vụ c Mó s: 62.44.01.13 LUN N TIN S HểA HC Ngi hng dn khoa hc: PGS TS o Quc Hng PGS TS Phan Th Ngc Bớch H NI 2015 Footer Page of 146 Header Page of 146 LI CAM OAN Tụi xin cam oan, õy l cụng trỡnh nghiờn cu ca riờng tụi di s hng dn ca PGS.TS o Quc Hng v PGS.TS Phan Th Ngc Bớch Hu ht cỏc s liu, kt qu lun ỏn l ni dung t cỏc bi bỏo ó v sp c xut bn ca tụi v cỏc thnh viờn ca th khoa hc Cỏc s liu, kt qu nghiờn cu c trỡnh by lun ỏn l trung thc v cha tng c cụng b bt k cụng trỡnh no khỏc H Ni, thỏng 12 nm 2015 Tỏc gi Nguyn Th Lan Hng Footer Page of 146 Header Page of 146 LI CM N Vi lũng kớnh trng v bit n sõu sc, tụi xin gi li cm n ti hai ngi Thy ca tụi l PGS.TS o Quc Hng v PGS.TS Phan Th Ngc Bớch, nhng ngi Thy ó ht lũng hng dn, giỳp v to mi iu kin thun li nht cho tụi hon thnh bn lun ỏn Cỏc Thy ó tn tỡnh ch bo tụi c v lnh vc khoa hc cng nh cuc sng S tn tõm dy bo ca cỏc Thy ó giỳp tụi ngy cng vng bc hn trờn ng nghiờn cu khoa hc m mỡnh ó la chn Trong quỏ trỡnh thc hin lun ỏn, tụi ó nhn c s giỳp nhit tỡnh ca cỏc cỏn b nghiờn cu thuc Vin Húa hc, Vin Hn lõm Khoa hc v Cụng ngh Vit Nam Nhõn dp ny tụi xin gi li cm n chõn thnh n cỏc cụ chỳ, anh ch em thuc Phũng Vụ c, Vin Húa hc, Vin Hn lõm Khoa hc v Cụng ngh Vit Nam, nhng ngi ó luụn giỳp , khớch l, ng viờn v dnh nhng tỡnh cm tt p cho tụi sut thi gian lm lun ỏn Tụi xin gi li cm n ti Ban lónh o Vin Húa hc, Phũng Qun lý Tng hp ó luụn quan tõm ti tin cụng vic v to mi iu kin thun li cho tụi hc tp, nghiờn cu v lm vic Tụi xin chõn thnh cm n Ban Ch nhim Khoa S phm Húa Sinh - K thut Nụng nghip, Ban Giỏm hiu Trng i hc ng Thỏp ó to mi iu kin thun li cho tụi v thi gian quỏ trỡnh hc nghiờn cu Tụi xin cm n Chng trỡnh Khoa hc v Cụng ngh trng im cp Nh nc Nghiờn cu, ng dng v phỏt trin cụng ngh sau thu hoch (KC.07/11-15) ca B Khoa hc v Cụng ngh ó h tr kinh phớ thc hin nghiờn cu ny Nhõn dp ny, tụi mun dnh nhng tỡnh cm sõu sc nht, trõn trng nht v xin kớnh tng thnh qu nh m tụi t c ti nhng ngi thõn gia ỡnh: Ba M - nhng ngi ó ht lũng nuụi dy tụi khụn ln, luụn ng viờn h tr tụi v mi mt, cỏc anh ch em ó chia s nhng khú khn, thụng cm v giỳp tụi Cui cựng tụi xin dnh nhng tỡnh cm c bit ti gia ỡnh nh thõn yờu ca tụi, ú l chng v gỏi tụi, nhng ngi ó luụn s chia, giỳp , cho tụi ngh lc v tinh thn hon thnh lun ỏn, l ngun ng viờn giỳp tụi vt qua mi khú khn v th thỏch cuc sng Tỏc gi Nguyn Th Lan Hng Footer Page of 146 Header Page of 146 MC LC Trang M U Chng TNG QUAN 1.1 Hydroxyapatit (HA - Ca10(PO4)6(OH)2) 1.1.1 Tỡnh hỡnh nghiờn cu, ng dng v phng phỏp iu ch 1.1.2 Tớnh cht .7 1.2 Polyme t nhiờn 1.2.1 Tinh bt (TB) 1.2.2 Maltodextrin (MD) 14 1.2.3 Alginat (Alg) .16 1.3 Vt liu composit HA/polyme 20 1.3.1 S to thnh vt liu composit HA/polyme .20 1.3.2 Cỏc phng phỏp tng hp composit HA/polyme 24 1.3.3 c trng ca vt liu composit HA/polyme 30 1.3.4 ng dng ca composit HA/polyme 34 Chng THC NGHIM V CC PHNG PHP NGHIấN CU .38 2.1 Húa cht v cỏc nguyờn liu u 38 2.2 Tng hp HA vựng nhit thp 42 2.3 Nghiờn cu tng hp cỏc composit HA/polyme 43 2.3.1 Composit HA/tinh bt (HA/TB) 43 2.3.2 Composit HA/tinh bt sn (HA/TBS) 45 2.3.3 Composit HA/maltodextrin (HA/MD) vi cỏc DE khỏc 45 2.3.4 Composit HA/alginat (HA/alg) v HA/oligoalginat (HA/olig) 46 2.4 Cỏc phng phỏp xỏc nh c trng 46 2.4.1 Phng phỏp nhiu x tia X (XRD) 46 2.4.2 Phng phỏp ph hng ngoi (FT-IR) .47 2.4.3 Phng phỏp hin vi in t quột (SEM) 47 2.4.4 Phng phỏp hin vi in t truyn qua (TEM) 48 2.4.5 Phng phỏp phõn tớch nhit (TGA-DTA) 48 2.4.6 Phng phỏp ph cng hng t ht nhõn (NMR) 49 Footer Page of 146 Header Page of 146 Chng KT QU V THO LUN .50 3.1 Tng hp HA bng phng phỏp kt ta vựng nhit thp 50 3.1.1 c trng XRD 50 3.1.2 c trng SEM 51 3.1.3 c trng FT-IR 53 3.1.4 c trng nhit 54 3.2 Nghiờn cu tng hp composit HA/tinh bt (HA/TB) 55 3.2.1 Phng phỏp trn HA bt 55 3.2.2 Phng phỏp trn HA huyn phự .59 3.2.3 Phng phỏp kt ta trc tip 71 3.2.4 So sỏnh hai phng phỏp tng hp vt liu composit HA/tinh bt (HA/TB) 88 3.3 Nghiờn cu tng hp composit HA/tinh bt sn (HA/TBS) 90 3.3.1 c trng XRD 90 3.3.2 c trng SEM v TEM .91 3.3.3 c trng FT-IR 93 3.3.4 c trng nhit 94 3.4 Nghiờn cu tng hp cỏc composit HA/maltodextrin (HA/MD) vi DE khỏc 95 3.4.1 Nghiờn cu tng hp cỏc composit HA/MD vi DE 12, 16, 20 v 25 95 3.4.2 nh hng ca t l thnh phn n cỏc c trng ca composit HA/MD vi DE 12 .99 3.4.3 So sỏnh cỏc composit HA/MD vi DE khỏc 105 3.5 Nghiờn cu tng hp composit HA/alginat (HA/alg) v HA/oligoalginat (HA/olig) 106 3.5.1 Nghiờn cu tng hp composit HA/alginat (HA/alg) .106 3.5.2 c trng cỏc oligome ca alginat 113 3.5.3 Nghiờn cu tng hp composit HA/olig 117 KT LUN V KIN NGH 122 DANH MC CC CễNG TRèNH KHOA HC CễNG B TI LIU THAM KHO PH LC Footer Page of 146 Header Page of 146 DANH MC CC Kí HIU V CH VIT TT Vit tt CaP: Canxi photphat DE: ng lng ng kh - Destrose Equivalent DP: polyme húa - Degree of Polymerization DTA: Phõn tớch nhit vi sai - Differential Thermal Analysis FT-IR: Ph hng ngoi bin i Fourier - Fourier Transform Infrared Spectroscopy GPC: Sc ký thm thu gel - Gel Permeation Chromatography HA: Hydroxyapatit - Ca10(PO4)6(OH)2 PDI: phõn tỏn lng phõn t - Polydispersity Index SEM: Hin vi in t quột - Scanning Electron Microscopy TEM: Hin vi in t truyn qua - Transmission Electron Microscopy TGA: Phõn tớch nhit trng lng -Thermal Gravimetric Analysis XRD: Nhiu x tia X - X-Ray Diffraction Kớ hiu alg: alginat D: Kớch thc tinh th trung bỡnh ca HA tớnh theo cụng thc Scherrer G: -L-guluronic M: -D-mannuronic MD: Maltodextrin Mw: Khi lng phõn t trung bỡnh olig: oligoalginat PVA: Poly(vinyl alcohol) PAA: Polyacrylic axit PCL: Poly (-caprolacton) TB: Tinh bt TBS: Tinh bt sn XC: tinh th ca HA Footer Page of 146 Header Page of 146 DANH MC BNG Bng 1.1 Trang Tớnh cht ca amyloz, amylopectin 11 Bng 2.1 Cỏc húa cht v nguyờn liu u s dng lun ỏn .38 Bng 2.2 ng lng ng kh (DE) ca cỏc polysaccarit 40 Bng 3.1 Kớch thc tinh th trung bỡnh v tinh th ca HA tng hp vựng nhit thp .51 Bng 3.2 Kớch thc trung bỡnh v tinh th ca HA mu HA v HT 56 Bng 3.3 Kớch thc trung bỡnh v tinh th ca HA cỏc mu composit HA/TB tng hp theo phng phỏp trn huyn phự 60 Bng 3.4 Kớch thc trung bỡnh v tinh th ca HA composit HA/TB tng hp cỏc nhit khỏc 65 Bng 3.5 Kớch thc trung bỡnh v tinh th ca HA mu HN v HE 66 Bng 3.6 Kớch thc trung bỡnh v tinh th ca HA composit HA/TB cú v khụng cú tỏc ng ca súng siờu õm 68 Bng 3.7 Kớch thc trung bỡnh v tinh th ca HA composit HA/TB c sy nhit v ụng khụ 69 Bng 3.8 Kớch thc trung bỡnh v tinh th ca HA cỏc mu composit HA/TB tng hp theo phng phỏp kt ta trc tip 72 Bng 3.9 S súng ca cỏc nhúm chc HA, TB v cỏc composit HA/TB 76 Bng 3.10 Kớch thc trung bỡnh v tinh th ca cỏc mu composit tng hp cỏc nhit khỏc 79 Bng 3.11 Kớch thc trung bỡnh v tinh th ca cỏc mu composit vi tc cp axit khỏc 82 Bng 3.12 Kớch thc trung bỡnh v tinh th ca HA ca cỏc mu composit HA/TB cú v khụng cú súng siờu õm 85 Bng 3.13 Kớch thc trung bỡnh v tinh th ca HA mu HD1 v HD2 87 Bng 3.14 Kớch thc v tinh th ca HA tng hp theo cỏc phng phỏp khỏc .88 Footer Page of 146 Header Page of 146 Bng 3.15 Kớch thc v tinh th ca HA cỏc mu composit HA/TBS .91 Bng 3.16 Kớch thc v tinh th ca cỏc composit HM12, HM16, HM20 v HM25 96 Bng 3.17 Kớch thc trung bỡnh v tinh th ca HA cỏc composit HA/MD 100 Bng 3.18 S súng c trng ca cỏc nhúm chc HA, MD v cỏc composit HA/MD 101 Bng 3.19 Kớch thc trung bỡnh v tinh th ca HA cỏc composit HA/alg .108 Bng 3.20 Footer Page of 146 Kt qu phõn tớch ph 1H-NMR ca alginat .116 Header Page of 146 DANH MC HèNH Trang Hỡnh 1.1 Cỏc dng hỡnh thỏi hc ca tinh th HA .7 Hỡnh 1.2 Cu trỳc ụ mng c s ca tinh th HA Hỡnh 1.3 Cu trỳc phõn t amyloz (a), amylopectin (b) 10 Hỡnh 1.4 nh hin vi quang hc ca ht tinh bt ngụ cỏc nhit khỏc quỏ trỡnh h húa [88] .13 Hỡnh 1.5 c trng cu trỳc ca alginat: a) Cỏc monome ca alginat; b) Cu trỳc chui, cu dng gh; c) Cỏc kiu phõn b cỏc mch alginat 16 Hỡnh 1.6 Mụ hỡnh liờn kt gia ion Ca2+ v alginat a) Mụ hỡnh to ht gel canxi alginat; b) Liờn kt ca block G vi ion canxi 18 Hỡnh 1.7 S to mm ca HA trờn cht nn polyme (a) Cỏc nhúm chc trờn phõn t polyme l cỏc v trớ to mm cho tinh th HA, (b) S to mm v phỏt trin tinh th HA trờn cỏc polyme c gn trờn Au 22 Hỡnh 1.8 Cu trỳc húa hc ca (a) mụ hỡnh hp trng ca canxi alginat, (b) mụ hỡnh hp trng vi cỏc ion tin cht cho s to mm HA v (c) cu trỳc hp trng khoỏng húa v (d) si nano composit HA/alginat tng hp trc tip .23 Hỡnh 1.9 S mụ t cỏc ht HA b mc kt vt lớ cht nn collagen (a) Theo nh SEM, HA kt cht nn collagen tng hp bng phng phỏp trn (b) 25 Hỡnh 1.10 S thớ nghim (a) v c ch (b) ca quỏ trỡnh EPD iu ch lp ph composit GO-HY-HA trờn cht nn Ti 27 Hỡnh 1.11 S ch to mng si composit HA/gelatin theo phng phỏp in xoay trũn .28 Hỡnh 1.12 S chuyn pha t brushit sang HA theo thi gian 31 Hỡnh 1.13 Gin DT-TGA ca cỏc vt liu composit HA/chitosan vi hm lng khỏc 32 Hỡnh 1.14 Cỏc dng hỡnh thỏi hc ca composit: ht micro (a), nano (b), khung xp (c), si (d), gin khung (e), mng a lp (f) 33 Footer Page of 146 Header Page 10 of 146 Hỡnh 2.1 Quy trỡnh iu ch oligome t alginat [118, 119] 40 Hỡnh 2.2 Phng phỏp tng hp HA t Ca(OH)2 v H3PO4 42 Hỡnh 2.3 S phng phỏp thc nghim tng hp composit HA/TB theo phng phỏp trn huyn phự 43 Hỡnh 2.4 S quy trỡnh thc nghim tng hp composit HA/TB theo phng phỏp kt ta trc tip .44 Hỡnh 3.1 Gin XRD ca cỏc mu HA tng hp -15, -10 v 0oC 50 Hỡnh 3.2 nh SEM ca cỏc mu HA tng hp vựng nhit thp 52 Hỡnh 3.3 Ph FT-IR ca mu HA tng hp 0oC 53 Hỡnh 3.4 Gin phõn tớch nhit ca mu HA tng hp 0oC 54 Hỡnh 3.5 Gin XRD ca HA, tinh bt (TB) v composit HA/TB (HT) 55 Hỡnh 3.6 nh SEM ca cỏc mu TB1, TB2, HA v HT 56 Hỡnh 3.7 Ph FT-IR ca HA, TB v composit HA/TB (HT) .57 Hỡnh 3.8 Gin phõn tớch nhit ca mu TB 58 Hỡnh 3.9 Gin phõn tớch nhit ca mu HT 58 Hỡnh 3.10 Gin XRD ca cỏc mu composit HA/TB tng hp theo phng phỏp trn huyn phự .60 Hỡnh 3.11 Ph FT-IR ca HA, tinh bt v cỏc composit tng hp bng phng phỏp trn huyn phự 61 Hỡnh 3.12 nh SEM ca cỏc composit HA/TB tng hp theo phng phỏp trn huyn phự .62 Hỡnh 3.13 nh TEM ca cỏc composit HA/TB tng hp theo phng phỏp trn huyn phự .63 Hỡnh 3.14 Gin phõn tớch nhit ca mu HT50 64 Hỡnh 3.15 Gin XRD ca cỏc mu composit HA/TB tng hp cỏc nhit khỏc .64 Hỡnh 3.16 nh SEM ca cỏc composit HA/TB tng hp cỏc nhit khỏc 65 Hỡnh 3.17 Gin XRD ca cỏc mu composit HA/TB tng hp dung mụi nc v etanol .66 Hỡnh 3.18 nh SEM ca cỏc composit HA/TB tng hp dung mụi nc v etanol 67 Hỡnh 3.19 Footer Page 10 of 146 Gin XRD ca cỏc mu HF v HF2 67 Header Page 141 of 146 39 E T Purdy K, Takii S, Nedwell D, Rapid extraction of DNA and rRNA from sediments by a novel hydroxyapatite spin-column method, Appl Environ Microbiol, 1996, 62, 3905-3907 40 Y Hashimoto, T Taki,T Sato, Sorption of dissolved lead from shooting range soils using hydroxyapatite amendments synthesized from industrial byproducts as affected by varying pH conditions, Journal of Environmental Management, 2009, 90(5), 1782-1789 41 Y Wang, L Liu, S Guo, Characterization of biodegradable and cytocompatible 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New Approach to Mineralization of Biocompatible Hydrogel Scaffolds: An Efficient Process toward 3Dimensional Bonelike Composites, Journal of the American Chemical Society, 2003, 125(5), 1236-1243 48 V M Rusu, C H Ng, M Wilke, B Tiersch, P Fratzl, et al., Size-controlled hydroxyapatite nanoparticles as self-organized organicinorganic composite materials, Biomaterials, 2005, 26(26), 5414-5426 128 Footer Page 141 of 146 Header Page 142 of 146 49 M Sadat-Shojai, M T Khorasani, E Dinpanah-Khoshdargi, A Jamshidi, Synthesis methods for nanosized hydroxyapatite with diverse structures, Acta Biomater., 2013, 9(8), 7591-621 50 V Uskokovic, D P Uskokovic, Nanosized hydroxyapatite and other calcium phosphates: chemistry of formation and application as drug and gene delivery agents, J Biomed Mater Res B Appl Biomater., 2011, 96(1), 152-191 51 M H Santos, M d Oliveira, L P d F Souza, H S Mansur, W L Vasconcelos, Synthesis control and characterization of hydroxyapatite prepared by wet precipitation 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Xác định đặc trưng đưa mối liên hệ đặc trưng composit HA /polyme thông số cấu trúc polyme  Nội dung luận án Để hoàn thành mục tiêu đề ra, luận án bao gồm nội dung nghiên cứu sau: Tổng hợp HA vùng... Vật liệu composit HA /polyme 20 1.3.1 Sự tạo thành vật liệu composit HA /polyme .20 1.3.2 Các phương pháp tổng hợp composit HA /polyme 24 1.3.3 Đặc trưng vật liệu composit HA/polyme