• 제목/요약/키워드: intermediates

검색결과 670건 처리시간 0.026초

Mechanistic insights of metal acetylacetonate-aided dehydrocoupling of liquid-state ammonia borane NH3BH3

  • Pereza, Manon;Mieleb, Philippe;Demirci, Umit B.
    • Advances in Energy Research
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    • 제4권2호
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    • pp.177-187
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    • 2016
  • Ammonia borane $NH_3BH_3$ solubilized in organic solvent is a potential liquid-state chemical hydrogen storage material. In this study, metal acetylacetonates like $Fe(O_2C_5H_7)_3$, $Co(O_2C_5H_7)_2$, $Ni(O_2C_5H_7)_2$, $Pd(O_2C_5H_7)_2$, $Pt(O_2C_5H_7)_2$ and $Ru(O_2C_5H_7)_3$ are considered for assisting dehydrocoupling of ammonia borane in diglyme (0.135 M) at $50^{\circ}C$. The molar ratio between ammonia borane and metal acetylacetonate is fixed at 100. A protocol for the separation of the soluble and insoluble fractions present in the slurry is proposed; it consists in using acetonitrile to make the precipitation of metal-based compounds easier and to solubilize boron-based intermediates/products. The nature of the metal does not affect the dehydrocoupling mechanisms, the $^{11}B\{^1H\}$ NMR spectra showing the formation of the same reaction intermediates. The aforementioned metal acetylacetonates do mainly have effect on the kinetics of dehydrocoupling. Dehydrocoupling takes place heterogeneously and dehydrogenation of ammonia borane in these conditions leads to the formation of polyborazylene via intermediates like e.g., B-(cyclodiborazanyl) amine-borane and borazine. Our main results are reported and discussed herein.

발현성 고혈압쥐의 관상순환 기능과 심장근의 에너지 대사에 관한 생체외 에너지원의 관류 연구 (Substrate-Perfusion Studies on Coronary Circulation and Myocardial Energy Metabolism in Spontaneously Hypertensive Rat Hearts)

  • 김은지
    • Journal of Nutrition and Health
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    • 제28권2호
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    • pp.115-126
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    • 1995
  • The effects of energy-yielding substrates on coronary circulation, myocardial oxygen metabolism, and intramyocytic adenylates of perfused Wistar control rat(WC) and spontaneously hypertensive rat(SHR) hearts were examined under basal and $\beta$-adrenergic stimulation conditions. The perfusion medium (1.0mM Ca2+) contained 5mM glucose (+5U/l insulin) in combination with 5mM pyruvate, 5mM lacate, 5mM acetate, or 5mM octanoate as energy substrates. Hearts were perfused with each substrate buffer for 20min under basal conditions. Coronary functinal hyperemia was induced by infusing for 20min isoproterenol (ISO, 1uM), a $\beta$-receptor agonist. Cardiac adenylates, glycolytic intermediates, and coronary venous lactate were measured by using an enzymatic analysis technique. Under basal conditions, acetate and octanoate significantly increased coronary flow(CF) of WC in parallel with myocardial oxygen consumption. However, CF of SHR was partly attenuated by coronary vasoconstriction despite metabolic acidosis. In addition, pyruvate and lactate depressd ISO-induced coronary functional hyperemia in SHR. It should be noted that octanoate exhibited coronary dysfunction under ISO conditions. On the other hand, fat substrates depleted myocardial high energy phosphate pool and accumulated breakdown intermediates. In SHR with coronary vasoconstriction under basal conditions, and with depressed coronary functional hyperemia, high energy phosphates were greatly depleted. These results suggest that energy substrates in the myocardium and coronary smooth muscle alter remarkably coronary circulation, and that coronary circulatory function is associated with a reserve of high energy phosphates and a balance between breakdown and nono synthesis of energy phosphates. These findings could be explained by alterations in the cytosolic redox state manipulated by LDH and hence in the cytosolic phosphorylation potential, which might be involved in hypertension of SHR.

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다환방향족탄화수소에 대한 오존처리의 방법에 관한 연구 (A Study on the Degradation of PAH in Organic and Aqueous Phases by Ozone)

  • 최영익;손희종;정철우
    • 한국물환경학회지
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    • 제22권6호
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    • pp.1123-1129
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    • 2006
  • 대부분의 polycyclic aromatic hydrocarbons (PAHs) 은 최우선 오염물질로 간주되어지고 있는 매우 유독한 물질이다. Pyrene은 PAHs들 중에서도 그 유독성은 가히 심각하다. 그리고 Pyrene과 다른 PAHs화합물들은 물에 잘 용해가 되지 않는 소수성 성질을 가지고 있어 화학적 또는 생물학적 분해가 용이하지 않다. 이러한 성질을 극복하기 위하여 본 연구에서는 Pyrene을 대표 물질로 하여 2 단계 오존처리를 하였다. 첫 단계에서 Pyrene을 무극성인 핵산 용매에 대량 (2000 mg/L) 으로 녹여 오존처리를 하였다. 이때 Pyrene은 극성 분자들, 즉 알콜과 알데하이드 그리고 에시드 기능기를 가지는 물질들로 변화되었으며 이 변화된 물질들을 다시 극성 용매, 물에 녹여 두 번째 오존처리를 하였다. 두 번째 오존 처리된 Pyrene의 부산물들과 중간생성물들은 생물학적 처리로 가능한지 연구되어지기 위해 $BOD_5$와 COD 그리고 E-coli toxicity tests가 이루어졌다. 그 결과 오존 처리된 Pyrene은 유독하지도 않았고 Pyrene의 부산물들과 중간생성물들은 생물학적 처리가 용이하여졌다. Gas chromatograph (GC) 분석을 통해 Pyrene의 부산물들과 중간생성물들을 밝혀내었다. 이 연구를 토대로 소수성 성질을 가지는 많은 방향족 물질들을 처리하기가 매우 용이해졌다.

Radical Intermediate Generation and Cell Cycle Arrest by an Aqueous Extract of Thunbergia Laurifolia Linn. in Human Breast Cancer Cells

  • Jetawattana, Suwimol;Boonsirichai, Kanokporn;Charoen, Savapong;Martin, Sean M
    • Asian Pacific Journal of Cancer Prevention
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    • 제16권10호
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    • pp.4357-4361
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    • 2015
  • Thunbergia Laurifolia Linn. (TL) is one of the most familiar plants in Thai traditional medicine that is used to treat various conditions, including cancer. However, the antitumor activity of TL or its constituents has never been reported at the molecular level to support the folklore claim. The present study was designed to investigate the antitumor effect of an aqueous extract of TL in human breast cancer cells and the possible mechanism(s) of action. An aqueous crude extract was prepared from dried leaves of TL. Folin-Ciocalteu colorimetric assays were used to determine the total phenolic content. Antiproliferative and cell cycle effects were evaluated in human breast adenocarcinoma MCF-7 cells by MTT reduction assay, cell growth inhibition, clonogenic cell survival, and flow cytometric analysis. Free radical generation by the extracts was detected using electron paramagnetic resonance spectroscopy. The exposure of human breast adenocarcinoma MCF-7 cells to a TL aqueous extract resulted in decreases in cell growth, clonogenic cell survival, and cell viability in a concentration-dependent manner with an $IC_{50}$ value of $843{\mu}g/ml$. Treatments with extract for 24h at $250{\mu}g/ml$ or higher induced cell cycle arrest as indicated by a significant increase of cell population in the G1 phase and a significant decrease in the S phase of the cell cycle. The capability of the aqueous extract to generate radical intermediates was observed at both high pH and near-neutral pH conditions. The findings suggest the antitumor bioactivities of TL against selected breast cancer cells may be due to induction of a G1 cell cycle arrest. Cytotoxicity and cell cycle perturbation that are associated with a high concentration of the extract could be in part explained by the total phenolic contents in the extract and the capacity to generate radical intermediates to modulate cellular proliferative signals.

금속염 함유 고분자형 키랄 살렌촉매에 의한 라세믹 에폭사이드의 광학선택적 비대칭 고리열림반응 (Asymmetric Ring Opening Reaction of Racemic Epoxides by Polymeric Chiral Salen Catalyst containing Metal Salts)

  • 이광연;카테카라울;김건중
    • 공업화학
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    • 제18권6호
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    • pp.562-567
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    • 2007
  • 키랄성 에폭사이드는 키랄중간체나 여러 출발물질로서 다양하게 이용되기 때문에 입체선택적인 합성방법은 학술적으로나 산업적인 관점에서 대단히 흥미롭다. 본 연구에서는 염화탈륨(III) 및 염화철(III)을 함유한 고분자형의 키랄성 코발트 살렌 촉매를 새로이 합성하고 그 특성을 평가하였다. 합성한 촉매는 여러 종류의 라세믹 에폭사이드 유도체의 가수분해의 속도차에 의한 비대칭 고리열림반응과 페놀 친핵체에 한 에폭사이드 산소 고리 열림반응에 적용하여 그 활성과 선택성을 조사하였다. 합성이 용이한 고분자구조의 살렌착체 촉매는 물과 페놀류를 친핵체로 하는 라세믹 에폭사이드의 고리 열림을 통하여 98% ee 이상을 나타낼 정도의 매우 높은 광학선택성을 보였다. 본 연구에서 적용한 촉매시스템은 키랄 에폭사이드, 1,2-디올 중간체 및 아릴옥시알코올 유도체의 제조에 매우 효과적이었다

Hybridization of Quercus aliena Blume and Q. serrata Murray in Korea - Analyses of Morphological variation and Flavonoid chemistry -

  • Park, Jin Hee;Park, Chong-Wook
    • 한국환경생태학회지
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    • 제29권2호
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    • pp.145-161
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    • 2015
  • This research was conducted in order to understand the hybridization between Quercus aliena Blume and Q. serrata Murray in Korea which show wide range of morphological variations within species and interspecific variations of diverse overlapping characteristics caused by hybridization. Morphological analysis (principal components analysis; PCA) of 116 individuals representing two species and their intermediates were performed. As a result, two species were clearly distinguished in terms of morphology, and intermediate morpho-types assumed to be hybrids between the two species were mostly located in the middle of each parent species in the plot of the principal components analysis. There was a clear distinction between two species in trichome distribution pattern which is an important diagnostic character in taxonomy of genus Quercus, whereas intermediate morpho-types showed intermediate state between two species' trichome distributions. Forty-two individuals representing two species and their intermediates were examined for leaf flavonoid constituents. Twenty-three flavonoid compounds were isolated and identified: They were glycosylated derivatives of flavonols, kaempferol, quercetin, isorhamnetin and myricetin. The flavonoid constituents of Q. aliena were five glycosylated derivatives: kaempferol 3-O-galactoside, kaempferol 3-O-glucoside, quercetin 3-O-galactoside, quercetin 3-O-glucoside, and Isorhamnetin 3-O-glucoside. The flavonoid constituents of Q. serrata had 20 diverse flavonol compounds including five flavonoid compounds found in Q. aliena. It was found that there is a clear difference in flavonoid constituents of Q. aliena and Q. serrata. Flavonoid chemistry is very useful in recognizing each species and putative hybrids. The flavonoid constituents of intermediates were a mixture of the two species' constituents and they generally showed similar characteristics to morpho-types. The hybrids between Q. aliena and Q. serrata showed morphologically and chemically diverse characteristics and it is assumed that there are frequent interspecific hybridization and introgression.

From L-Ascorbic Acid to Protease Inhibitors: Practical Synthesis of Key Chiral Epoxide Intermediates for Aspartyl Proteases

  • Chang, Sun-Ki;So, Soon-Mog;Lee, Sang-Min;Kim, Min-Kyu;Seol, Kyoung-Mee;Kim, Sung-Min;Kang, Jae-Sung;Choo, Dong-Joon;Lee, Jae-Yeol;Kim, B.-Moon
    • Bulletin of the Korean Chemical Society
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    • 제33권7호
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    • pp.2213-2218
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    • 2012
  • Efficient synthetic routes were developed to prepare a sizable amount (4-15 grams) of the chiral epoxides 4-6 as versatile intermediates for the synthesis of aspartyl protease inhibitors of therapeutic interest such as HIV protease and ${\beta}$-secretase. Oxidative cleavage of the C(2)-C(3) double bond of L-ascorbic acid followed by functional group manipulation led to the preparation of the epoxide 10, which was opened with an azide to yield a common aziridine intermediate 12. Through opening of the aziridine ring of 12 with either a carbon or a sulfur nucleophile, chiral epoxide precursors 4-6 could be prepared for various HIV protease inhibitors. Except for the final low melting epoxides 5 and 6, all intermediates were obtained as crystalline solids, thus the synthetic pathway can be easily applied to a large-scale synthesis of the chiral epoxides.

Cu wire 촉매를 이용한 촉매습식과산화공정에 의한 1,4-다이옥산의 분해 (1,4-Dioxane Decomposition by Catalytic Wet Peroxide Oxidation using Cu Wire Catalysts)

  • 이동근;김둘선
    • 청정기술
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    • 제22권4호
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    • pp.281-285
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    • 2016
  • 난분해성 1,4-다이옥산을 분해시키기 위하여 촉매습식과산화반응에 활성적인 Cu wire촉매를 사용하였다. Cu wire 촉매를 사용함으로써 1,4-다이옥산의 완전한 분해가 가능하였으나, 분해된 1,4-다이옥산은 완전 무기화($CO_2$$H_2O$로 전환)되지 못하고 중간생성물인 ethylene glycol diformate, oxalic acid, formic acid, formaldehyde, acetaldehyde 등으로 전환되었다. 1,4-다이옥산이 분해되어 없어짐에 따라 formaldehyde와 oxalic acid가 점진적으로 나타나기 시작하여 증가하다가 최고농도를 보인 후 다시 감소하였다. 이들 두 중간체의 최고농도 도달시점에 acetaldehyde의 농도가 급격히 증가하여 최고농도를 보인 후 다시 감소하였다. 이들 세가지 중간물질의 감소와 함께 ethylene glycol diformate, formic acid가 생성되기 시작하여 그 농도가 점진적으로 증가하였다. 이들은 연속적인 과정을 통해 생성되었다. Cu wire 촉매는 반응이 진행되는 동안 활성이 떨어지지 않고 매우 안정적이었다.

N-Alkyl-N-Nitrosocarbamoyl-3$\alpha$-Amino-와 3$\beta$-Amino-5$\alpha$-Cholestane 유도체들의 합성 및 항암작용 평가 (Synthesis and Antitumor Evaluation of N-Alkyl-N-Nitrosocarbamoyl-$\alpha$-Amino- and 3$\beta$-Amino-$\alpha$-Cholestane Derivatives)

  • 김정균;최순규;조인섭;유동식;유성호;문경호
    • 약학회지
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    • 제29권2호
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    • pp.62-69
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    • 1985
  • The isomeric intermediates, $3{\alpha}$and $3{\beta}-amino-5{\alpha}-cholestane required for the synthesis of N-nitrosoureas, N-(2-chloroethyl)-N-nitrosocarbamoyl-$3{\alpha}-amino-5{\alpha}$-cholestane (9), N-methyl-N-nitrosocarbamoyl-3${\alpha}-amino-5{\alpha}-cholestane$ (10), N-(2-chloroethyl)-N-nitrosocarbamoyl-$3{\beta}-amino-5{\alpha}-cholestane$: (7), and N-methyl-N-nitrosocarbamoyl-$3{\beta}-amino-5{\alpha}-cholestane$ (8) were obtained through the $LiAlH_{4}$ reduction of $5{\alpha}$-cholestan-3-one oxime, followed by the chromatographic separation: the assignment of the stereochemistry of both isomers were based on the shape and chemical shift of $C_{3}$-proton resonances on their NMR spectra and on the elution mobility on the TLC. The urea intermediates, N-(2-chloroethyl) carbamoyl-3.alpha.-amino-5.alpha.-cholestane (13), N-methylcarbamoyl-$3{\alpha}-amino-5{\alpha}-cholestane$ (14), N-(2-chloroethyl) carbamoyl-$3{\beta}-amino-5{\alpha}-cholestane (11) and N-methyl-$3{\beta}-amino-5{\alpha}$-cholestane (12) were prepared by the treatment of each isomers ($3{\alpha}$-amino-and $3{\beta}-amino-5{\alpha}$-cholestane) with alkyl isocyanates in anhydrous $CHCl_{3}$, and the corresponding nitrosoureas, 7-10 were obtained by the nitrosation of the ureas, 11-14, with AcOH (or HCOOH)/$NaNO_{2}$ in ice-cold condition. The inhibitory activity of the nitrosoureas, 7-10, and their intermediates, 12-14 towards the growth of L1210 murine leukemia cells, were examined. Among them, the compounds 9 and 10 exhibited high activity having $ED_{50}$ to be 5.5g/ml and 6.1g/ml, respectively.

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자침(刺鍼)이 마취(痲醉)에 미치는 작용기전(作用機轉) 연구(硏究) (제(第) 2 보(報)) (A Study on the Effect of Acupuncture on Anesthesia and the Mode of Action (The Second Report))

  • 박희수;박경식
    • Journal of Acupuncture Research
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    • 제19권4호
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    • pp.140-151
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    • 2002
  • This study was carried to identify whether acupuncture at several meridian points can affect the human anesthesia or not through the analysis of serum intermediates, such as, melatonin, serotonin, TSH, cortisol in human serum. We investigated the effect of accupuncture on the change of serum intermediates which have frequently been made a subject of discussion owing to its hyponic and sedative properties in practice. The result obtained were as follow ; 1. Serum melatonin levels was hardly affected at 40 minutes after general acupuncture on Hab-Gog, Nae-Gwan, and the other meridian points as compared with that($5.64{\pm}1.02pg/ml$) of resting control group. But on day 1 after acupuncture, these tend to increase significantly ($7.95{\pm}2.05pg/ml$ to $8.21{\pm}1.57pg/ml$, p <0.05). On the other hand, control group under sleep showed the serum level of $7.39{\pm}1.03pg/ml$. Additional acupuncture at In-Dang induced the increased melatonin level, especially at 40minutes after acupuncture(p <0.05). 2. Serotonin level in resting control serum recorded $51.14{\pm}8.17{\mu}g/ml$. Acupuncture at determined meridian point intend to increase average level of serotonin, but not significant. However observation on day 1 after acupuncture at Hab-Gwan meridian point and under sleeping showed the significantly increased serotonin level, $74.05{\pm}35.83{\mu}g/ml$, $70.44{\pm}13.08{\mu}g/ml$, respectively. 3. TSH level in intact human serum recorded $0.85{\pm}0.24{\mu}IU/ml$. and the serum exposed to acupuncture showed the irregular pattern of TSH level in a mean range of $0.76{\pm}0.44{\mu}IU/ml$ to $1.06{\pm}0.38{\mu}IU/ml$, regardless of meridian point or time after acupuncture. 4. The values of serum cortisol in control group were $11.76{\pm}2.06{\mu}g/dl$ in resting, $7.51{\pm}2.85{\mu}/dl$ under sleep, respectively. The level of serum cortisol in 40minutes after acupuncture was markedly (p <0.05) reduced to the serum levels of $5.65{\pm}2.58{\mu}g/dl$ (Hab-Gog, Nae-Gwan), $7.58{\pm}3.21{\mu}g/dl$ (Gyo-Gam, Sin-Mun besides Hab-Gog, Nae-Gwan), $6.43{\pm}3.54{\mu}g/dl$ (In-Dang besides to Hab-Gog, Nae-Gwan), respectively, as compared with control, intending to increase a little on day 1 after acupuncture. From the above results, the analysis of serum intermediates suggest that acupunctuation at meridian points applied to at this study act upon the phase of light anaesthesia or hypnosis, at the same time affect pituitary-adrenal axis rather than hypothalamus-pituitary axis in the secretary system of hormone and also don't affect dorsal-raphe nucleus according to the observation of change transition in serum intermediates, such as TSH, serotonin, and cortisol.

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