• Title/Summary/Keyword: NMR Spectroscopy

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Properties of the High and Low Molecule of the Proteoglycan Extracted from Ganoderma lucidum IY009 (Ganoderma lucidum IY009 배양균사체 유래 단백다당류의 저분자와 고분자 분획의 특성)

  • Baek, Seong-Jin;Kim, Yong-Seuk;Chun, Uck-Han;Lee, Eun-Sook;Lee, June-Woo
    • The Korean Journal of Mycology
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    • v.29 no.1
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    • pp.1-8
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    • 2001
  • To examine the structural properties of the proteoglycan (GMPG, Ganoderma lucidum mycelial proteoglycan) obtained from mycelia in Ganoderma lucidum IY009, we obtained the low and high molecular proteoglycan by ultrafiltration and sepharose CL-4B column chromatography. The physicochemical properties of these fractions were as follows. When the proteoglycan separated by ultrafiltration and sepharose CL-4B column chromatography, its was not fractionated completely. The molecular weight of high molecular proteoglycan by the gel column chromatography (CH) was 250 kD and 2,000 kD, and low molecular proteoglycan was 12kD. The total carbohydrate was consisted of 75.7% (UH) and 96.7% (CH), and the low fraction was 72.7% (UL) and 87.1% (CL), respectively. The sugar of high and low molecular proteoglycan composed of glucose, mannose, fructose, galactose, xylose, ribose and arabinose. Glucose contents of all fraction were ranged from $46.9%{\sim}82.4%$ of the total sugar and the ratio of ${\alpha}$\;and\;{\beta}-glucose$ was $0.84{\sim}1.14$, and its indicated the proteoglycan to be ${\beta}-glucan$. Amino acids pattern showed that the fractions contained a large amount of aspartie acid, glutamic acid, alanine and leucine. These fractions showed the characteristics of IR absorption for ${\beta}-glucan$ at $890\;cm^{-1}\;and\;^{13}C-NMR$ spectroscopy showed the presence of the ${\beta}-1,3-glucan$ and a ${\beta}-1,6-glucan$.

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Synthesis and Properties of Molybdenum and Tungsten Oxo-Nitrosyl Complexes of Methylthioamidoxime (산소-니트로실 착물의 연구(제3보): 티오메틸아미드옥심의 몰리브덴과 텅스텐 산소-니트로실 착물의 합성과 특성)

  • Roh, Soo Gyun;Oh, Sang Oh
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.28-36
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    • 1996
  • The pentanuclear complexes have been obtained by the reactions of molybdenum(VI) and tungsten(VI) polynuclear complexes with molybdenum(O) and tungsten(O) dinitrosyl mononuclear complexes, and methylthioamidoxime. The prepared complexes (n-Bu4N)2[Mo4O12Mo(NO)2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2](1), (n-Bu4N)2[W4O12Mo(NO)2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2](2), (n-Bu4N)2[Mo4O12W (NO)2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2] (3) have been characterized by elemental analysis, infrared, UV-visible and 1H NMR spectra. The complexes are elucidated the cis-{M(NO)2}2+(M = Mo, W) unit and a slight delocalization by spectroscopy. The structure of (n-Bu4N)2[W4O12Mo(NO) 2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2] was determined by X-ray single crystal diffraction. Crystal data are follows: Monoclinic, $P21}a$, a = 22.14(2) $\AA$, b = 14.93(1) $\AA$, c = 23.20(1) $\AA$, $\beta$ = 111.08(6) $\AA$, V = 7155(9) $\AA$, Z = 4, final R = 0.072 for 6191(I > $3\sigma(I)).$ The structure of complex forms two dinuclear [W2O5{CH3SCH2C(NH2)NHO}{CH3SCH2C(NH)NO}] and a central {Mo(NO)2} 2+ core. The geometric structure of the {Mo(NO)2} 2+unit is the formally cistype and C2v symmetry.

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Stability Constants of Nitrogen-Oxygen Donor Macrocyclic Ligand-Metal Ion Complexes in Aqueous Solutions (질소-산소 주개 거대고리 화합물-금속착물의 수용액에서의 안정도상수)

  • Jeong Kim;Chang-Ju Yoon;Hyu-Bum Park;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.35 no.2
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    • pp.119-127
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    • 1991
  • The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

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Inhibitory Effect of Scopoletin Isolated from Sorbus commixta on TNF-α-Induced Inflammation in Human Vascular Endothelial EA.hy926 Cells through NF-κB Signaling Pathway Suppression (마가목 수피에서 분리한 scopoletin의 EA.hy926 혈관내피세포에서 NF-κB 신호전달을 통한 TNF-α로 유도된 혈관염증 저해 효과)

  • Kang, Hye Ryung;Kim, Hyo Jung;Kim, Bomi;Kim, Sun-Gun;So, Jai-Hyun;Cho, Soo Jeong;Kwon, Hyun Sook
    • Journal of Life Science
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    • v.30 no.4
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    • pp.343-351
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    • 2020
  • Sorbus commixta Hedl. has traditionally been used as a remedy for cough, asthma, and other bronchial disorders. In this study, three major triterpenoids-lupeol, β-sitosterol, and ursolic acid and a coumarin, scopoletin, were isolated from a CHCl3-soluble fragment of the bark of S. commixta. Their structures were identified by spectroscopic analyses, including mass spectrometry (MS), 1D-, and 2D- nuclear magnetic resonance spectroscopy (NMR), as well as by comparing the data with data reported in the literature. Scopoletin was isolated from this plant for the first time. It is a nutraceutical compound contained in many plants that has been reported to exert diverse biological activities, including anti-inflammatory effects. This study examined the inhibitory effect of scopoletin on TNF-α-induced vascular endothelial inflammation. Unlike the marginal impact of other compounds against low-density lipoprotein (LDL) oxidation and vascular endothelial inflammation, scopoletin showed remarkable activity on LDL oxidation (IC50 = 10.2 μM) and exerted vascular anti-inflammatory effects in EA.hy926 human endothelial cells activated by TNF-α. It suppressed the expression of adhesion molecules, such as ICAM-1, VCAM-1, and E-selectin, and blocked the adhesion between THP-1 monocytes and EA. hy926 endothelial cells. It also inhibited TNF-α-induced NF-κB translocation from the cytosol to the nucleus. Moreover, IκBα phosphorylation, which was increased by TNF-α treatment, was reduced after treatment with scopoletin. Thus, scopoletin inhibited TNF-α-induced vascular inflammation in endothelial cells by suppressing the NF-κB signaling pathway. These results demonstrate that owing to its anti-inflammatory activity in the vascular endothelium, scopoletin has the potential to inhibit atherosclerosis development.

A Study on the Fouling of Ultrafiltration Membranes Used in the Treatment of an Acidic Solution in a Circular Cross-flow Filtration Bench (순환식 막 모듈 여과장치를 이용한 산성용액의 수처리 공정 시 발생하는 한외여과막 오염에 관한 연구)

  • Kim, Nam-Joon;Choi, Chang-Min;Choi, Yong-Hun;Lee, Jun-Ho;Kim, Hwan-Jin;Park, Byung-Jae;Joo, Young-Kil;Kang, Jin-Seok;Paik, Youn-Kee
    • Membrane Journal
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    • v.19 no.3
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    • pp.252-260
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    • 2009
  • The effects of the treatment of an acidic solution at pH 2 on polyacrylonitrile ultrafiltration (UF) membranes were investigated using a circular cross-flow filtration bench with a membrane module. A substantial reduction in the membrane permeability was observed after 80 hours' treatment of the acidic solution. In addition, the analyses of the sample solutions by ultraviolet/visible absorption spectroscopy and gas chromatography/mass spectrometry (GC/MS), which were taken from the feed tank as a function of the treatment time, showed that a new organic compound was produced in the course of the treatment. From a thorough search of the mass spectral library we presumed the new compound to be 1,6-dioxacyclododecane-7,12-dione (DCD), one of the well-known additives for polyurethane. Based on further experimental results, including the scanning electron microscope (SEM) images and the solid-state NMR spectra of the membranes used for the treatment of the acidic solution, we suggested that the decrease of the permeate flux resulted not from the deformation of the membranes, but from the fouling by DCD eluted from the polyurethane tubes in the filtration bench during the treatment. Those results imply that the reactivity to an acidic solution of the parts comprising the filtration bench is as important as that of the membranes themselves for effective treatments of acidic solutions, for efficient chemical cleaning by strong acids, and also in determining the pH limit of the solutions that can be treated by the membranes.

Spectroscopic Characterization of Soil Humic Acid Fractions by Molecular Weight (토양에서 추출한 흄산의 분자량별 분류에 따른 분광학적 성질 비교)

  • Shin, Hyun Sang;Moon, Hichung;Yang, Han Beom;Yun, Sock Sung
    • Journal of the Korean Chemical Society
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    • v.39 no.1
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    • pp.66-70
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    • 1995
  • The soil humic acid was subdivided into four subfractions by molecular weight (F1: >100.000 dalton; F2: >100.000 dalton; F3: >10.000 dalton; F4: >2.000 dalton) using MP-dual hollow fiber ultrafiltration system. The characterization using IR, 1H and 13C NMR spectroscopy, showed similar spectroscopic features of HA, demonstrating that the bulk properties of HA subfractions are very similar to one another. IR spectral data showed a decrease in polysaccharide contents and increase in carboxylate functionality as molecular weight become smaller.functions. The structure of (NO) can be described by two interactions (N${\cdot}{\cdot}{\cdot}$N, N${\cdot}{\cdot}{\cdot}$O). One is the ONNO structure with an (N${\cdot}{\cdot}{\cdot}$N) interaction. In this structure, acyclic cis-ONNO with $C_{2v}$-symmetry, acyclic trans-ONNO with $C_{2h}$, and cyclic ONNO with trapezoidal structure ($C_{2v}$) are optimized at the MP2 level. The other structure is the ONON structure with an (N${\cdot}{\cdot}{\cdot}$O) interaction. In the structure, acyclic cis-ONON with Cs$^{-symmetry}$ and cyclic ONON of the rectangular ($C_{2h}$), square $(D_{2h})$, rhombic $(D_{2h})$, and parallelogramic $(D_{2h})$ geometries are also optimized. It is found that acyclic cis-ONNO $(^1A_1$) is the most stable structure and cyclic ONNO ($^3A_1$) is the least stable. Acyclic trans-ONNO ($^3A_1$) with an (N${\cdot}{\cdot}{\cdot}$N) interaction, acyclic trans-ONON and bicyclic ONON $(C_{2v})$ with (N${\cdot}{\cdot}{\cdot}$O) interaction, and acyclic cis- and trans-NOON with an (O${\cdot}{\cdot}{\cdot}$O) interaction can not be optimized at the MP2 level. Particularly, acyclic trans-ONNO with $C_{2h}$-symmetry can not be optimized at the CCSD(T) level. Meanwhile, acyclic NNOO ($^1A_1$, $C_s)$ and trianglic NNOO ($^1A_1$,$C_{2v})$ formed by the (O${\cdot}{\cdot}{\cdot}$N) interaction between $O_2$and $N_2$are optimized at the MP2 level. The binding energies and the relative energy gaps among the isomers are found to be relatively small./sec. Spiral CT scans during the arterial phase were obtained 35 seconds after the injection of contrast medium. CT findings of 78 lesions less than 4cm in diameter were correlated with angiographic findings. Results : The attenuation of lesions was high(n = 69), iso(n = 5), and low(n = 4) compared with liver parenchyma during the arterial phase of spiral CT. In lesions with high-, iso-, and low-attenuation during the arterial phase of spiral CT, hypervascularity on angiograms was found in 63 of 69(91.3%), three of five(60%), and three of four lesions(75%), respectively. Six lesions with high-attenuation on the arterial phase of spiral CT were not seen on angiography. Two iso-attenuated and one low-attenuated lesion were hypovascular on angiograms. Conclusion : The results of this study suggest that with some exceptions there was good correlation between the arterial phase of spiral CT and angiography.

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Chemical and Spectroscopic Characterization of Peat Moss and Its Different Humic Fractions (Humin, Humic Acid and Fulvic Acid) (피트모스에서 추출한 휴믹물질(휴믹산, 풀빅산, 휴민)의 화학적 및 분광학적 물질특성 규명)

  • Lee Chang-Hoon;Shin Hyun-Sang;Kang Ki-Hoon
    • Journal of Soil and Groundwater Environment
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    • v.9 no.4
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    • pp.42-51
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    • 2004
  • Peat humin(p-Humin), humic acid(p-HA) and fulvic acid(p-FA) were isolated from Canadian Sphagnum peat moss by dissolution in 0.1M NaOH followed by acid precipitation. After purification cycles, they are characterized for their elemental compositions and, acid/base properties. Functionalities and carbon structures of the humic fractions were also characterized using FT-IR and solid state $^{13}C$-NMR spectroscopy. Those results are compared with one another and with soil humic substances from literatures. Main purpose of this study was to present a chemical and spectroscopic characterization data of humic substance from peat moss needed to evaluate its environmental applicability. The relative proportions of the p-Humin, p-HA and p-FA in the peat moss was $76\%,\;18\%,\;and\;3\%$, respectively, based on the total organic matter content ($957{\pm}32\;g/kg$). Elemental composition of p-Humin were found to be $C_{1.00}H_{1.52}O_{0.79}N_{0.01}$ and had higher H/C and (N+O)/C ratio compared to those of p-HA($C_{1.00}H_{1.09}O_{0.51}N_{0.02}$) and p-FA($C_{1.00}H_{1.08}O_{0.65}N_{0.01}$). Based on the analysis of pH titration data, there are two different types of acidic functional groups in the peat moss and its humic fractions and their proton exchange capacities(PEC, meq/g) were in the order p-FA(4.91) >p-HA(4.09) >p-Humin(2.38). IR spectroscopic results showed that the functionalities of the peat moss humic molecules are similar to those of soil humic substances, and carboxylic acid(-COOH) is main function group providing metal binding sites for Cd(II) sorption. Spectral features obtained from $^{13}C$-NMR indicated that peat moss humic molecules have rather lower degree of humification, and that important structural differences exist between p-Humin and soluble humic fractions(p-HA and p-FA).

Neurochemical Profile Quantification of Regional Adult Mice Brain Using: ex vivo $^1H$ High-Resolution Magic Angle Spinning NMR Spectroscopy (생체 외 조직 고 분해능 Magic Angle Spinning을 이용한 정상 Adult Mice에서의 뇌 부위별 뇌 신경화학 대사물질 정량분석)

  • Lee, Do-Wan;Woo, Dong-Cheol;Lee, Sung-Ho;Kim, Sang-Young;Kim, Goo-Young;Rhim, Hyang-Shuk;Choi, Chi-Bong;Kim, Hwi-Yool;Lee, Chang-Wook;Choe, Bo-Young
    • Progress in Medical Physics
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    • v.21 no.1
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    • pp.35-41
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    • 2010
  • The purpose of this study is to quantitate regional neurochemical profile of regional normal adult mice brain and assess regional metabolic differences by using ex vivo $^1H$ high-resolution magic angle spinning nuclear magnetic resonance spectroscopy ($^1H$ HR-MAS NMRS). The animals were matched in sex and age. The collected brain tissue included frontal cortex, temporal cortex, thalamus, and hippocampus. Quantitative 1D spectra were acquired on 40 samples with the CPMG pulse sequence (8 kHz spectral window, TR/TE = 5500/2.2 ms, NEX = 128, scan time: 17 min 20 sec). The mass of brain tissue and $D_2O$+TSP solvent were 8~14 mg and 7~13 mg. A total of 16 metabolites were quantified as follow: Acet, NAA, NAAG, tCr, Cr, tCho, Cho, GPC + PC, mIns, Lac, GABA, Glu, Gln, Tau and Ala. As a results, Acet, Cho, NAA, NAAG and mIns were showed significantly different aspects on frontal cortex, hippocampus, temporal cortex and thalamus respectively. The present study demonstrated that absolute metabolite concentrations were significantly different among four brain regions of adult mice. Our finding might be helpful to investigate brain metabolism of neuro-disease in animal model.

Antifungal activities of coumarins isolated from Angelica gigas and Angelica dahurica against Plant pathogenic fungi (당귀와 백지로부터 분리한 Coumarin계 물질들의 식물병원균에 대한 항균활성)

  • Ryu, Shi-Yong;Kim, Young-Sup;Kim, Heung-Tae;Kim, Seong-Ki;Choi, Gyung-Ja;Kim, Jeoung-Seob;Lee, Seon-Woo;Heor, Jung-Hee;Cho, Kwang-Yun;Kim, Jin-Cheol
    • The Korean Journal of Pesticide Science
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    • v.5 no.3
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    • pp.26-35
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    • 2001
  • In order to search potent antifungal substances from domestic plants, 40 plants cultivated in Korea were collected. After extracting with methanol (MeOH) and concentrating to dryness, the MeOH extracts were screened for in vivo antifungal activity against six plant diseases at a concentration of $2000{\mu}g/mL$. Fourteen extracts showed disease-controlling activity more than 90% against at least one of the 6 plant diseases tested; eight, seven, and three extracts controlled more than 90% the development of rice blast, tomato late blight, and wheat leaf rust, respectively. However, none of the extracts exhibited in vivo antifungal activity more than 90% against rice sheath blight, tomato gray mold, and barley powdery mildew. From the MeOH extracts of Angelica gigas and A. dahurica showing potent controlling activity against rice blast, 1 and 2 antifungal substances, respectively, were isolated by solvent partitioning and column chromatography. The three compounds were identified to be coumarins, namely, decursin, imperatorin, and isoimperatorin, by mass spectrometry and NMR spectroscopy. They were examined for in vitro and in vivo antifungal activities together with umbelliferone (7-bydroxycournarin) and scopoletin (6-methoxy-7-hydroxycoumarin) containing a free hydroxyl group at position 7 to investigate the structure-activity relationship. In vitro, most of 50% growth inhibitory concentrations ($IC_{50}$) were over $200{\mu}g/mL$, indicating that they have relatively weak antifungal activity. The antifungal activity of decursin and scopoletin, containing cyclic alkoxy groups instead of free hydroxyl group at position 7, was stronger than umbelliferone and scopoletin. Especially, decursin and imperatorin showed potent antifungal activities against Pythium ultimum and Magnaporthe grisea, respectively, with $IC_{50}$ values less than $25{\mu}g/mL$. In vivo, decursin and imperatorin showed potent antifungal activity against rice blast, whereas other coumarins hardly controlled the development of 6 plant diseases tested. These results suggest that the antifungal activity of 7-hydroxycoumarin derivative is substantially increased when the hydroxyl group at position 7 is protected by a stable cyclic alkoxy grouping.

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Purification and Biological Activity of Ecdysterone from Korean Achyranthes radix (韓國産 牛膝의 Ecdysterone 抽出과 그 生理活性에 관한 硏究)

  • Kim, Jeong-Il;Lee, Jae-Yong;Kim, Chun-Su;Park, Kwang-E.
    • Journal of Sericultural and Entomological Science
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    • v.25 no.1
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    • pp.1-20
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    • 1983
  • It has been known that the insect molting hormone and its analogues exist also in plant kingdom and their concentration has been found to be about 0.1~2.0% of dry matter, which is equivalent to $10^3{\sim}10^5$ times of those in insects. This study was carried out; 1) to isolate the phytoecdysones from Korean Achyranthes radix and characterize their physico-chemical properties. 2) to investigate the biological activity of this phytoecdysone on Bombyx mori larvae. The resuls were summarized as follows; 1. The extraction method of phytoecdysones was optimized by three consecutive reflux for 1hr using 200g of dried and milled radix per 1l methanol. 2. The purification from the crude extract was made by a series of steps such as precipitation of gum-type polymer with n-Butyl acetate, adsorption on technical grade silica and chromatography with neutral alumina. The conditions of each step were optimized and the resulting crude crystal was about 500mg per kg dry radix. 3. The crude crystal from the cultivated Achyranthes(Achyranthes japonia) contained ecdysterone (20-hydroxyecdysone) and inokosterone in the proportion of one to one. In order to separate these, a series of processes such as acetylation, separation by alumina column chromatography deacetylation by alcoholysis, deionization and crystallization were introduced and optimized 125mg of ecdysterone and 18mg of inokosterone per kg dry radix were thus obtained. 4. The wild Achyranthes (Achyranthes obtusifolia) radix was found to contain the ecdysterone only. A 285mg of ecdysterone was crystallized per kg dry radix. 5. Isolated ecdysterone, inodosterone and acetylated compounds were characterized by IR., UV., NMR spectroscopy, mp, TLC and densitometry. 6. Ligation experiment was undertaken to confirm the biological activity of the purified ecdysterone; the ecdysterone could induce larval-pupal metamorphosis in the ligated abdomen of 4th instar larvae injecting 0.5~1.0${\mu}g$. 7. By ecdysterone feeding experiment using artificial diet, it was elucidated that the critical time of feeding would be the first half of each instar resulting in increased weight of silk layer. 8. The ecdysterone was fed to 5th instar silkworm at the level of 1, 2, 3, 5ppm of dry feed of artificial diet containing 5% mulberry leaves for 72hrs. At 2ppm of the concentration. body weight and silk layer weight were arrived at maximum. But at higher concentrations body weight and silk layer weight decreased than the control group. At 2ppm of the concentration, body weight was increased by 12.5%. 9. Feeding 2ppm of ecdysterone at the later half of 5th instar, the duration of larvae was shortened.

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