몇 가지 키토산 비드들의 물리화학적 특성에 관한 연구

하병조,이옥섭,이윤식 ( Byung Jo Ha,Ok Sub Lee,Yoon Sik Lee ) 한국공업화학회 1996 공업화학 Vol.7 No.1

몇 가지 키토산 비드들을 W/O 에멀젼법과 capillary extrusion법에 의해 제조하여, SEM 사진을 통해 표면 구조와 표면적의 차이를 관찰하였고, BET법으로 표면적을 측정하였으며, 피크린산 적정에 의해 유효 아민함량을 측정하여 상기 결과들과의 상관관계를 알아 보았다. W/O 에멀젼법에 의해 제조한 비드의 경우 capillary extrusion법에 의해 제조된 비드들보다 입자의 크기가 작았으며, 반대로 표면적, 유효 아민함량은 높게 나타났다. 또한 비드의 표면적, 유효 아민함량, 겉보기 밀도(apparent density) 및 기계적 강도(hardness)는 제조시 건조방법에 따라 매우 큰 편차를 나타내었다. Hardness 측정결과 solvent dehydration법에 의해 건조된 비드들이 동결건조법에 의해 건조된 비드들에 비해 높은 강도를 나타내었다. 또한 겉보기 밀도에 있어서도 solvent dehydration한 비드들이 동결건조한 비드들에 비해 높은 걸보기 밀도를 보였다. SEM 사진 분석결과 solvent dehydration법에 의한 비드들은 매우 작은 pore들이 비드의 표면에 무수히 존재한 반면 동결건조한 비드에서는 벌집모양의 pore들이 존재하고 있음을 알 수 있었다. 피크린산 적정결과 solvent dehydration한 비드의 경우 동결건조한 비드보다 약 10배의 높은 유효 아민함량을 나타내었으며 비드의 표면적이 클수록 유효 아민함량은 높게 나타났다. 또한 fluorescamine을 반응시킨 후 형광현미경으로 관찰하여 비드의 표면과 내부의 pore 주위에 노출된 1차 아민의 존재를 정성적으로 확인할 수 있었다. Several chitosan beads were prepared by W/O emulsion and capillary extrusion methods. The surface structures were observed through SEM pictures, the surface areas were determined by BET method, the available amine contents were measured by picric acid titration method, and the results were correlated each other. The beads from W/O emulsion method were smaller in size but had higher hardness, surface area, and available amine contents than the ones from capillary extrusion method. Moreover, the surface area, available amine contents, apparent density and the hardness showed large differences according to the drying processes. As compared between the solvent dehydration and the freeze drying technique in W/O emulsion method, the former showed higher surface area, higher available amine contents and hardness than the latter. SEM pictures revealed that in case of solvent dehydration method, very small pores existed, whereas in case of freeze drying method, cell-like pores existed on the surface. The results of picric acid titration showed that the beads dried by solvent dehydration method were 10 times higher in amine contents than those from freeze drying method, and the amount of amine contents were increased as the surface area was increased. After fluorescamine was reacted with chitosan beads, the fluorescence labeled beads were observed through fluorescence microscope. The results showed that most of primary amine existed on the surface of beads and pores.

Novel Synthesis and Biological Properties of GHK - Chitosan Conjugate

하병조,이옥섭,이윤식 ( Byung Jo Ha,Ok Sub Lee,Yoon Sik Lee ) 한국공업화학회 1995 한국공업화학회 연구논문 초록집 Vol.1990 No.3

PPG-β-cyclodextrin에 의한 Aesculetin의 분자 캡슐화와 화장품에의 적용

하병조 대한미용학회 2022 대한미용학회지 Vol.18 No.1

Aesculetin, a derivative of coumarin, is a compound known as a scavenger of reactive oxygen species (ROS). Aesculetin is also known to have various inhibition effects for cyclooxygenase (COX) as well as matrix metalloproteinases (MMPs). However, limited solubility and labile color stability were the main problems in cosmetic formulation. Therefore, the purpose of this study was to improve limited solubility and color stability using a molecular capsulation technique. PPG-β-CD, polypropylene glycol-β-cyclodextrin, can form non-covalent inclusion complexes by molecular capsulation. Inclusion complex by PPG-β-CD is a unique approach to molecular capsulation based on molecular selectivity. In this study, PPG-β-CD was prepared by substitution of the hydroxyl groups under high pressure conditions. Fourier-transformed infrared spectroscopy (FT-IR) was used for determination of the chemical structure of PPG-β-CD. A deep freezing method under high vacuum was used for molecular capsulation. UV/VIS spectroscopy, scanning electron microscope (SEM), and X-ray diffraction (XRD) were used for structural confirmation of the molecular capsule. UV/VIS spectroscopy showed a bath-chromic shift. SEM showed a swollen shape and XRD showed the non-crystalline structure of aesculetin. These findings indicate that molecular capsulation was completed between aesculetin and PPG-β-CD. The molecular capsulation between PPG-β-CD and aesculatin enhanced the solubility and color stability of aesculetin in formulation of skin care cosmetics. The results suggested that by use of PPG-β-CD the molecular capsule could be a multi-functional ingredient for use in cosmetic products.

Characteristics of the Cellulose Make-up Powder Dyed with Flavanone-glycoside and Mordants

하병조 대한미용학회 2020 대한미용학회지 Vol.16 No.3

This present study investigated cellulose make-up powder dyed with flavone-glycoside and mordants. Cosmetic make-up powder celluloses were modified with flavanone-glycoside to produce several different colored powders. To achieve this purpose, flavanone-glycoside was obtained from citrus peel using marceration and soxhlation methods. The structure of flavanone-glycoside was examined by Fourier transform infrared spectroscopy (FT-IR) and Liquid Chromatography/Mass Spectroscopy (LC/MS). Two types of cellulose make-up powders were modified with flavanone-glycoside and several mordants. Ag, Fe, Mg, Al, and Ca ions were chosen for mordanting as they are the major elements among cationic metal ions. The dyed cellulose powder was prepared by applying different types of mordant through a simultaneous mordanting process. The results indicated that flavanone-glycoside could be linked to the cellulose powder through coordination bonding with mordants. The type of mordant affected the CIE L*a*b* system and color depth of the cellulose powder. The color difference ΔE values for cellulose dyed powder increased as follows: Al < Ca < Mg < Fe < Ag ions. For ethyl cellulose dyed powder, the color difference ΔE values increased as follows: Ca < Al < Mg < Fe < Ag ions. It is concluded that cellulose derivatives modified with mordants and flavanone-glycoside can be a make-up powder having various colors.ity.

메틸 바이올렛이 함유된 키토한 마이크로 캡슐의 제조와 그 방출특성

하병조,이옥섭,이윤식 ( Byung Jo Ha,Ok Sub Lee,Yoon Sik Lee ) 한국공업화학회 1995 공업화학 Vol.6 No.5

에멀젼 상분리법과 글루타르알데히드를 사용한 가교반응에 의해 메틸바이올렛이 함유된 키토산 마이크로캡슐을 제조하였다. 이들의 제조를 위해 먼저 수상/유화제/유기상으로 이루어진 W/O 에멀젼을 형성시킨 후 에멀젼의 안정도에 미치는 요소들에 대해 조사하였다. 유기상이 톨루엔인 경우 솔비탄 모노올레이트 (HLB=4.3)를 사용했을 때 상대적으로 높은 유화안정성을 나타내었다. 또한 보조계면활성제로 n-헥산올을 첨가해 줌으로써 유화안정성이 상승적으로 증가함이 관찰되었다. 제조된 마이크로캡슐의 내부를 전자현미경을 통해 관찰한 결과 약 8㎛ 정도의 표피층이 발견되었으며, 마이크로캡슐의 평균 입자크기는 약 250㎛이었다. 마이크로캡슐의 pH변화에 따른 팽윤부피를 관찰한 결과 산성조건 (pH=3)일수록 높은 팽윤성을 나타내었으며, 알칼리조건 (pH=9)에서는 팽윤이 거의 일어나지 않음을 알 수 있었다. 또한 양성자성 용매가 비양성자성 용매에 비해 상대적으로 높은 팽윤성을 보였다. 한편 키토산 마이크로캡슐에 함유된 메틸바이올렛의 방출거동을 pH 변화 및 lysozyme 존재하에서 관찰한 결과, pH 5.1의 초산염 완충용액에서 lysozyme을 첨가한 경우 가장 높은 방출현상을 나타내었다. Crosslinked-chitosan microcapsules containing methyl violet were prepared by emulsion phase separation method. The factors influencing the stability of W/O emulsions, composed of water phase/emulsifier/organic phase were examined. Sorbitan monooleate (HLB=4.3) showed higher emulsion stability in water/toluene system. The addition of n-hexanol as cosurfactant synergistically increased the emulsion stability. A typical microcapsules had a mean diameter of 250㎛ with a skin layer of 8㎛. The swelling volumes at different pH indicated that the degree of swelling increases in acidic condition, but not in alkaline condition. Also, the swelling volumes in protic solvents showed relatively higher than in aprotic solvents. Release of methyl violet from the microcapsules was also examined at different pH conditions with or without lysozyme. The results showed that the addition of lysozyme to the suspension medium at pH 5.1 acetate buffer gave the highest release rate of methyl violet.

키토산 올리고당의 향장학적 효과에 관한 연구

하병조 凡石學術奬學財團 1998 凡石學術論文集 Vol.2 No.1

천연고분자인 키틴으로부터 비교적 분자량이 낮은 키토산을 합성한 후 이를 아질산을 이용하여 가수분해시켜 보습, 세포증식, 라디칼 제거 및 미백과 같은 향장학적 효과가 있는 키토산 올리고당을 제조하였다. 얻어진 키토산 올리고당은 중합도가 2~6이었으며 MBTH 시약을 이용하여 말단의 알데히드가 수산기로 전환되었음을 확인할 수 있었다. 또한 흡습 및 수분보유능을 글리세린과 비교 측정한 결과, 상대습도 43%와 81%에서 글리세린은 시간 변화에 따라 지속적으로 흡습성이 증가되는 경향을 나타내었으나, 키토산 올리고당의 경우 10시간 이후 3~5%의 거의 일정한 흡습성을 보였다. 반면, 상대습도 43%에서 키토산 올리고당의 수분보유능을 측정한 결과 글리세린과 유사한 결과를 나타내었다. 키토산 올리고당의 섬유아세포 증식효과는 1×10^(-3)~1×10^(-4)%에서 관찰되었으며, 자유라디칼 제거활성(SC_(50))은 3200 ppm이었다. 이외에 키토산 올리고당은 멜라닌 생성을 억제시킬 수 있을 뿐 아니라 물과 알코올에 대한 용해성이 있어 기능성 화장품의 원료로 효과적으로 사용될 수 있을 것으로 여겨진다. Chitosan oligosaccharide having cosmetic effect, such as moisturizing effect, cell proliferation, free radical scavenging activity, and whitening effect was prepared by NaNO_(2) oxidation-NaBH_(4) reduction from natural chitosan. After deamination by NaNO_(2) oxidation, the resulting aldehyde group was reduced to 2, 5-anhydro-D-mannitol unit, and the reduction was checked by MBTH reagent. The resulting chitosan oligosaccharide showed a degree of polymerization(DP) 2-6 by G PC analysis. Water absorption test at relative humidity of 43% and 81% showed lower moisture absorption ability when compared with glycerine. but water holding capacity at relative humidity of 43% was similiar to glycerine. Cell proliferation of dermal fibroblasts was showed in the range of 1 × 10^(-3)~1 × 10^(-4)%. and free radical scavenging activity(SC_(50)) was 3200 ppm. Chitosan oligosaccharide also showed the inhibitory effect on melanogenesis of melanoma cells.

압박 고나사의 생역학적 특성과 골반 골절 정복을 위한 임상적 의의

하병조,최성훈,박상수 한국생체재료학회 2012 생체재료학회지 Vol.16 No.1

Load-displacement diagram of a compression hip screw (CHS) was obtained both by a mechanical method, as suggested in ASTM F384, and by a finite element analysis and the results were compared with each other. The two displacement values agreed with each other within 0.15 mm when the compression load was varied from 200 to 1,400 N. The study showed that maximum of 1.1 mm compression bending deformation of the CHS could occur when a patient stands on a single leg with the CHS, and that mechanical failure of the CHS could occur when the load exceeds 1,500 N. Good adhesion of the CHS with the femoral bone is required to prevent side effects of the procedure such as sliding and/or cut-off of the lag screw. Various techniques of surface treatment of the lag screw are suggested for better adhesion of CHS and femoral head.

연구논문 - 유기 / 정밀 : W / O 에멀젼법에 의한 Hydroxypropyl Chitosan 비드의 합성과 특성에 관한 연구

하병조,이옥섭,이윤식 한국공업화학회 1996 한국공업화학회 연구논문 초록집 Vol.1994 No.1

Hydroxypropyl Chitosan Microspheres Containing Platinum Complex by O/O Emulsion Solvent Evaporation Method and Their Releasing Properties

하병조 한국키틴키토산학회 2007 한국키틴키토산학회지 Vol.12 No.2

Microspheres containing cis-(DACH)PtCl2, cis-diaminocyclohexanedichloroplatinum(II) were prepared from hydroxypropylin vitro release profile of platinum complex. For this purpose,hydroxypropyl chitosan(HPCH) was synthesized by chitosan and propylene oxide under alkaline catalyst. FT-IR and solid statecross polarization/magic angle spinning(CP/MAS) 13C-NMR confirmed the incorporation of hydroxypropyl moieties on chitosan.The degre of substitution of HPCH was 3.5 by elemental analysis. Wide angle X-ray difraction(WAXD) pattern of HPCHshowed lower crystallinity than that of chitosan. The physical properties such as solubility, hydrophilic character, and thermalsolubilities in several organic solvents, compared with chitosan. Homogeneous DMF solution of HPCH and cis-(DACH)PtCl2 waspoured into liquid paraffin containing sorbitan monooleate as a emulsifier, followed by solvent evaporation at 40oC for 48 hr.Microspheres with a mean diameter of 130m and a spherical shape were obtained. Initial loading content of cis-(DACH)PtCl2 inthe microspheres was 11% and the loading content was 9.9±0.15%. Loading yield was about 90±1.4%. The release of cis-(DACH)PtCl2 from the microspheres in 0.1M phosphate buffer, pH 7.4, approximately followed pseudo-first order kinetics.

Swelling Properties of Some Modified Chitosan Beads

하병조,유병희,이옥섭,이윤식 한국공업화학회 1995 한국공업화학회 연구논문 초록집 Vol.1994 No.1