초록 ▼

제 1 과제 굴껍질로부터 칼슘의 회수 및 이용 1. 굴껍질을 회수하여 여러 깨끗이 수세한 다음 건조한 후 마쇄하여 온도가 1200℃인 전기로에서 회화(灰火)시킴으로써 고순도의 칼슘화합물(산화칼슘)을 회수하였다. 2. 회수한 칼슘화합물을 염산(HCl)과 반응시켜 염화칼슘(CaCl/sub 2/)을 제조하였으며, 또한 인산수소나트륨(Na/sub 2/HPO/sub 4/)과 반응시킴으로써 인산화칼슘도 제조하였다. 3. 굴껍질로부터 회수한 칼슘을 체내의 흡수를 증가시키기 위하여 단백질(어피젤라틴) 가수분해물과 당(키토산)의 가수분해물인 올리공

제 1 과제 굴껍질로부터 칼슘의 회수 및 이용 1. 굴껍질을 회수하여 여러 깨끗이 수세한 다음 건조한 후 마쇄하여 온도가 1200℃인 전기로에서 회화(灰火)시킴으로써 고순도의 칼슘화합물(산화칼슘)을 회수하였다. 2. 회수한 칼슘화합물을 염산(HCl)과 반응시켜 염화칼슘(CaCl/sub 2/)을 제조하였으며, 또한 인산수소나트륨(Na/sub 2/HPO/sub 4/)과 반응시킴으로써 인산화칼슘도 제조하였다. 3. 굴껍질로부터 회수한 칼슘을 체내의 흡수를 증가시키기 위하여 단백질(어피젤라틴) 가수분해물과 당(키토산)의 가수분해물인 올리공당을 도입시킨 결과, 흡수효과가 약 50∼70% 증가된 것을 in vitro법에 의해 확인하였다. 4. In vivo법에서 굴껍질 유래 칼슘화합물과 어피 젤라틴 가수분해물 및 키토산 올리고당을 함께 칼슘을 결핍시킨 흰쥐(rat)에 투여한 결과, 흰주의 성장 과정중 부적절한 대사 이상 증세는 전혀 발견되지 않았으며, 대퇴골 강도는 탄산칼슘을 섭취시킨 대조군에 비해 각각 12% 및 20% 증가되는 효과를 보였으며, 또한 뇨 및 분으로의 칼슘 배설은 각각 50% 이하로 감소된 것으로 나타났다. 이러한 거스로 보아 부작용이 없는 체내 칼슘원이라 판단되었다. 제2과제 어뼈 유래의 천연 수산화아파타이트를 이용한 바이오 세라믹스 소재 개발 1. 원료어로는 우리 나라의 수산 가공식품으로 대량적으로 사용되고 있는 참치뼈를 원료로 선정하였다. 참치뼈에 부착된 단백질을 알칼리 처리 및 효소 처리로 제거하고, 남은 어뼈 성분을 850∼1350℃로 회화시켜 추출한 수산화의 고유 물성을 조사한 결과, X-선 분석에서 Ca/sub 10/(PO/sub 4/)/suv 6/(OH)/suv 2/의 조성을 가지는 수산화아파타이트 상으로 나타났다. 입자 크기 분포상의 관찰에서 회화온도는 1050℃ 이하가 가장 적당할 것으로 판단되었다. 입자의 변화양상을 SEM으로 추적한 결과 입자형상의 변화는 나타나지 않았다. 이러한 결과는 참치뼈로부터 추출한 수산화 아파타이트가 생체재료로써 충분한 이용가능성을 가지고 있음을 보여주었다. 2. 참치뼈로부터 추출한 수산화아파타이트 자체의 소결체와 강도 증가를 위하여 첨가한 wallostonite와의 고상반응법으로 얻은 소결체의 각각의 특성을 검토하였다. 수산화아파타이트 자체보다는 wallostonite와 무게비로 1:1 혼합한 것을 1300℃에서 소결처리하여 제조된 소결체가 가장 양호한 것으로 나타났다. X-선 관찰에서 주 결정상은 수산화아파타이트였고 wallostonite가 부결정상인 바이오세라믹스로 관찰되었다. 그러나 그 강도는 17.91±0.19 MPa로서 해면골(cancellous bone)의 강도인 10∼20 MPa과 유사하였으나, 관절연골(articular cartilage)의 최대강도인 40 MPa에는 미치지 못하였다. 3. 앞의 결과에서 강도의 개선을 위하여 수산화아파타이트에 wallastonite 및 글래스세라믹스를 첨가한 복합체를 제조하여 그 특성을 검토하였다. X-선 분석 결과 복합체들의 결정상은 psedowallostonite(α-CaSiO/sub 3/)와 tricalcium phosphate(β-TCP)로 나타났다. 그러나 수산화아파타이트의 분해에 따른 TCP의 생성 때문에 수산화아파타이트의 피크는 관찰되지 않았다. 수산화아파타이트에 wallostonite와 CaO-P/sub 2/O/sub 5/-CaF/sub 2/-SiO/sub 2/-MgO계 세라믹스(35:35:30)의 강도는 소결온도가 1200℃에서 81.21±1.49 MPa으로 강도면에서는 크게 개선되었다. 이는 관절연골의 최대강도인 40 MPa보다도 우수하였다. 4. 참치뼈로부터 추출한 수산화아파타이트를 출발물질로 이용하여 제조한 복합 소결체가 인공체액 중에서 소결체 간의 결합이 이루어질 것인가를 SEM을 통하여 관찰하여 in vitro에서의 친화성을 검토하였다. 사용된 모든 시료에 대하여 결합이 형성됨을 보였다. 수산화아파타이트의 함량이 상대적으로 높은 세라믹스는 전형적인 잎모양의?? 있었다. 그리고 햄스터를 통한 in vivo 실험에서도 부작용은 거의 없는 것으로 나타났다.

Abstract ▼

1. Recovery and Utilization of Calcium from Oyster Shell : Approximately 210 thousand tons of oyster are annually harvested in Korea. Oyster shell, more than 90% of oyster content, wasted and induced a serious environmental pollution. However, oyster shell contains a large quantity of calcium mainly

1. Recovery and Utilization of Calcium from Oyster Shell : Approximately 210 thousand tons of oyster are annually harvested in Korea. Oyster shell, more than 90% of oyster content, wasted and induced a serious environmental pollution. However, oyster shell contains a large quantity of calcium mainly composed of calcium carbonate. Therefore, oyster shell can be used as a calcium supplement. Bioavailability of calcium compounds was investigated using calcium compounds in oyster shell. To this end, calcium oxide was prepared by burning of oyster shell at high temperature. Calcium compounds such as calcium chloride(CaCl/sub 2/) and calcium phosphate(CaHPO/sub 4/) were prepared by the calcium oxide. Then, the calcium compounds used experimented to in vitro and in vivo for testing bioavability in body. The results from the present study were summarized as follows. 1. The structure and purity of oyster shell burnt in various temperatures were analyzed by X-ray, SEM, and EDS, and the optimum temperature was tobe 1200℃. On the basis of this result, calcium compounds, CcCl/sub 2/ and CaHPO/sub 4/, were prepared from the oyster shell burnt in 1200℃. 2. In the in vitro experiment using fish skin gelatin peptides(FSGP) and chitosan oligo saccharides(COS) as calcium-absorption promoting supplement for calcium compounds from oyster shell, FSGP and COS showed the highest hindrance effect against calcium phosphate. They were 70% and 50% more effective than those in control, respectively. 3. In the in vivo experiments of the calcium-absorption activation, the groups taken only calcium compounds from oyster shell showed almost the same effect as the control group, used calcium carbonate. However, those groups showed higher effects on the weight and strength of femur and showed tendency to some extent preventing the formation of insoluble calcium phosphate in intestine. 4. The groups taken the calcium compounds from oyster shells and FSGP showed significantly higher amounts of calcium and ash than those of the control group. Especially, the groups taken 3% FSGP as supplement were better than those of 1% FSGP. Furthermore, the higher absorption effect was observed not in the groups taken calcium chloride but in the groups taken calcium phosphate. 5. The groups taken calcium compounds with COS showed lower weight increase and food efficiency than those of the control group. However, they were better in the bone strength and in the amount of ash and calcium. Contrast to the groups taken FSGP, the groups taken 1% COS showed better affected, and the groups taken CaCl/sub 2/ were even better affected than the groups taken CaHPO/sub 4/. These results suggest that calcium compounds from oyster shell could be used as an effective dietary calcium source. 2. Development of Bioceramics Material Using Hydroxyapatite from Fish Bone For the effective utilization of the fish bone waste from seafood industry, the physical properties of the isolated hydroxyapatite from tuna bone has been investigated. On X-ray measurements, the phase of the bone calcined by various temperatures were identified as hydroxyapatite, Ca/sub 10/(PO/sub 4/)/sub 6/(OH)/sub 2/. The mean particle size distribution was changed as functions of temperatures. However, the particle shape was a geometrically non-regular type. These trends are consistent with SEM images. The composition of the bioceramic batch by calcined tuna bone were not perfectly agreed with the suggested data, but the partially substituted composition possibly has shown the application of it as a bioceramic materials. In order to study sintering properties of hydroxyapatite isolated from tuna bone, the hydroxyapatite-containing wollastonite(CaO·SiO/sub 2/) sintered by solid state reaction has been investigated. The degree of sintering at the weight ratio, 1 : 1(hydroxyapatite : wollastonite) was good at 1350℃. The endothermic curves due to dehydration of moisture were identified at 80℃ and the exothermic curves as α-Ca/sub 3/(PO/sub 4/)/sub 2/ phases nearby 1200℃ and 1300℃ on the DSC analysis, respectively. On X-ray measurements, the major phases of hydroxyapatite-containing wollastonite by solid state reaction were identified as hydroxyapatite and pseudowollastonite. These phases are close to the bioactive phase known as the A-W(Apatite-Wollastonite) glass-ceramics. The microstructure containing many porosities on SEM images was not changed by increasing sintering temperatures. The maximum strength of specimen prepared by solid state reaction was 17.91 0.19 MPa as a 4-point bending method and this value was close to the strength of cancellous bone, 10∼20 MPa. The properties of composites consisted of the hydroxyapatite : wollastonite : bio-glasses(35 : 35 : 30) were studied. The major phases were identified as pseudowollastonite and tricalcium phosphate(TCP), respectively. These phases were differ from the solid-state reaction matters For the glass-ceramic prepared by using hydroxyapatite, the major phases were identified as pseudowollastonite and tricalcium phosphate(TCP), respectively. The measured maximum strength was 90.05 0.05 MPa at 1200℃ for 3hr. This value was lower than themaxinum strength of frame bone of cortical bone, as 50-150 MPa. However, the bending strenghtof glass-ceramic as more enhanced than other methods. The replacement of skeletal bone like a cortical bone in human body was possible by controlling treatment conditions and particle sizes. The replacement of skeletal bone like a cortical bone in human body was possible by controlling treatment conditions and particle sizes. Chemical bonding was investigated in simulated body fluid for several selected hydroxyapatite-containing comp0osites. The hydroxyapatite-containing composites chemically bonded each other in Ringer's solution for 4 weeks. The bonding mechanism in simulated body fluid is heterogeneous nucleation and growht on the interface between two sintered bodies. In order to develop the test of safety evaluation of hydroxyapaptite powder which will be used as dental materials originated from tuna fish, oral mucous membane irritation tes was carried out. Oral mucous membrane test was studied with syrian hamsters which were injected as dosw of 5 g/kg B.W. with hydroxyapatite under pentobarbital sodium anesthesia. Each animal's left cheek pouch was everted and cleaned, and the samples were loosely placed at the bottom of the pouch with a double-suture techique for14 days. Hamsters of control group wer same treated without inserting the hydroxylapatite powder. Any abnormal clinical signs in both treated and control pouchs were not observed for 14 days. There were no significant differences in mean body weight changes between contrel and treated hamsters. Any particular changes in hamster oral mucous mombrane of both treatment and control group were not detected. To evaluate the acute toxicity of hydroxyapatite powder isolated from tuna bone in Sparague-Dawley via subcutaneous routes, the study was performed. Hydroxyapatite powder was deministered at dose levels of 5, 2.5, 1.25, 0.625 0.3125 and 0 g/kg. After single subcutaneous admistration to SD rats of both sexes, we obseved rats for 14 days. Hydroxyapatite powder in the acute toxicity study did not induce any toxic signs in the rats in mortalities, clinical findings, body weights and gross findings. In viwew of result, it is impossible to estimate LD50 values in rats. Therefore, it was concluded that hydroxyapatite have no effect on acute toxicity and side effect in rats.

목차 Contents

• 제1세부과제 굴껍질로부터 칼슘의 회수 및 이용...25
• 제1장 서론...27
• 제2장 재료 및 방법...30
• 제1절 재료...30
• 제2절 방법...31
• 제3장 결과 및 고찰...40
• 제4장 요약...80
• 제5장 참고문헌...82
• 제2세부과제 어뼈 유래의 수산화아파타이트를 이용한 바이오 세라믹스 소재의 개발...87
• 제1장 참치뼈로부터 추출한 천연Hydroxyapatite의 특성...89
• 제2장 건식법으로 분쇄한 Hydroxyapatite 및 Wollastonite가 첨가된 소결체의 특성...120
• 제3장 습식법에 의한 Hydroxyapatite 소결체의 특성...138
• 제4장 바이오 글래스가 첨가된 Hydroxyapatite 복합체 및 Glass-Ceramicss의 특성...153
• 제5장 인공체액에서의 Hydroxyapatite 세라믹 복합체간의 결합...178
• 제6장 참치뼈로부터 추출한 Hydroxapatite의 랫드에 대한 급성피하 독성시험...198
• 제7장 참치뼈로부터 추출한 Hydroxyapatite의 햄스터에 대한 구강점막자극시험...214
• 제8장 종합고찰...227
• 제9장 종합요약...235