• 제목/요약/키워드: intermediates

검색결과 669건 처리시간 0.025초

Constant Correlation Factors between Temkin and Langmuir or Frumkin Adsorption Isotherms at Poly-Pt, Re, and Ni/Aqueous Electrolyte Interfaces

  • Chun Jang H.;Jeon Sang K.;Chun Jin Y.
    • 전기화학회지
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    • 제7권4호
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    • pp.194-200
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    • 2004
  • The constant correlation factors between the Temkin and the Langmuir or the Frumkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) for the cathodic H2 evolution reaction (HER) at poly-Pt and Re/0.5M $H_2SO_4$ and poly-Ni/0.05 M KOH aqueous electrolyte interfaces have been experimentally and consistently found using the phase-shift method. At intermediate values of the fractional surface coverage $(\theta),\;i.e.,\;02<{\theta}<0.8$, the Langmuir and Temkin adsorption isotherms of OPD H for the cathodic HER are correlated to each other even though the adsorption conditions or processes are different from each other. At the same range of $\theta$, correspondingly, the Frumkin and Temkin adsorption isotherms of OPD H for the cathodic HER are correlated to each other. The equilibrium constants $(K_o)$ for the Temkin adsorption isotherms $({\theta}\;vs.\; E)$ are consistently ca. 10 times greater than those (K, Ko) for the corresponding Langmuir or Frumkin adsorption isotherms ($({\theta}\;vs.\; E)$. The interaction parameters (g) for the Temkin adsorption isotherms $({\theta}\;vs.\; E)$ are consistently ra. 4.6 greater than those (g) for the corresponding Langmuir or Frumkin adsorption isotherms $({\theta}\;vs.\; E)$. These numbers (10 times and 4.6) can be taken as constant correlation factors between the corresponding adsolftion isotherms (Temkin, Langmuir, Frumkin) at the interfaces. The Temkin adsorption isotherm corresponding to the Langmuir or the Frumkin adsorption isotherm, and vice versa, can be effectively verified or confirmed using the constant correlation factors. Both the phase-shift methodand constant correlation factors are useful and effective for determining or confirming the suitable adsorption isotherms (Temkin, Langmuir, Frumkin) of intermediates for sequential reactions in electrochemical systems.

Alcohol and Temperature Induced Conformational Transitions in Ervatamin B: Sequential Unfolding of Domains

  • Kundu, Suman;Sundd, Monica;Jagannadham, Medicherla V.
    • BMB Reports
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    • 제35권2호
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    • pp.155-164
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    • 2002
  • The structural aspects of ervatamin B have been studied in different types of alcohol. This alcohol did not affect the structure or activity of ervatamin B under neutral conditions. At a low pH (3.0), different kinds of alcohol have different effects. Interestingly, at a certain concentration of non-fluorinated, aliphatic, monohydric alcohol, a conformational switch from the predominantly $\alpha$-helical to $\beta$-sheeted state is observed with a complete loss of tertiary structure and proteolytic activity. This is contrary to the observation that alcohol induces mostly the $\alpha$helical structure in proteins. The O-state of ervatamin B in 50% methanol at pH 3.0 has enhanced the stability towards GuHCl denaturation and shows a biphasic transition. This suggests the presence of two structural parts with different stabilities that unfold in steps. The thermal unfolding of ervatamin B in the O-state is also biphasic, which confirms the presence of two domains in the enzyme structure that unfold sequentially. The differential stabilization of the structural parts may also be a reflection of the differential stabilization of local conformations in methanol. Thermal unfolding of ervatamin B in the absence of alcohol is cooperative, both at neutral and low pH, and can be fitted to a two state model. However, at pH 2.0 the calorimetric profiles show two peaks, which indicates the presence of two structural domains in the enzyme with different thermal stabilities that are denatured more or less independently. With an increase in pH to 3.0 and 4.0, the shape of the DSC profiles change, and the two peaks converge to a predominant single peak. However, the ratio of van't Hoff enthalpy to calorimetric enthalpy is approximated to 2.0, indicating non-cooperativity in thermal unfolding.

산, 염기 이원기능 금속-유기 구조체 촉매를 이용한 알돌 축합반응 (Aldol Condensation over Acid-Base Bifunctional Metal-Organic Framework Catalysts)

  • 정영민
    • 청정기술
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    • 제20권2호
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    • pp.116-122
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    • 2014
  • 수열합성 또는 후처리 방법을 통해 산 또는 염기능을 나타내는 다양한 종류의 이원기능 금속-유기 구조체 물질을 제조하여 대표적인 방향제 원료 중 하나인 자스민알데하이드(jasminaldehyde)를 합성하기 위한 벤즈알데하이드(benzaldehyde, $C_6H_5CHO$)와 헵탄알(heptanal, $C_6H_{13}CHO$)의 알돌 축합반응의 촉매로 활용하였다. 실험 결과, 산 또는 염기점 모두에서 축합반응이 진행되었으며, 촉매 성능은 기능기의 도입 여부 및 종류와 금속-유기 구조체의 물리적인 특성에 크게 의존하였다. Jasminaldehyde 선택도는 황산 기능기를 도입한 경우에는 금속-유기 골격체의 종류에 상관없이 감소하였으나, 아민 기능기를 도입한 경우에는 금속-유기 골격체의 종류에 따라 상반된 경향을 나타내었다. 평가한 촉매 중 MIL-101의 촉매 성능이 가장 우수하였는데, 이러한 결과는 MIL-101이 알돌 축합반응의 촉매로 작용하기에 충분한 산량과 적당한 산세기를 가지고 있으며, 세공 크기가 넓어 크기가 큰 생성물의 물질이동 측면에서 유리하기 때문인 것으로 판단된다.

$Co_2$ Corrosion Mechanism of Carbon Steel in the Presence of Acetate and Acetic Acid

  • Liu, D.;Fu, C.Y.;Chen, Z.Y.;Guo, X.P.
    • Corrosion Science and Technology
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    • 제6권5호
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    • pp.227-232
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    • 2007
  • The corrosion behavior of carbon steel (N80) in carbon dioxide saturated 1%NaCl solution with and without acetic acid or acetate was investigated by weight-loss test, electrochemical methods (polarization curve, Electrochemical impedance spectroscopy). The major objective is to make clear that the effect of acetic acid and acetate on the corrosion of carbon steel in $Co_2$ environments. The results indicate that either acetic acid or acetate accelerates cathodic reducing reaction, facilitates dissolution of corrosion products on carbon steel, and so promotes the corrosion rate of carbon steel in carbon dioxide saturated NaCl solution. All Nyquist Plots are consisting of a capacitive loop in high frequency region, an inductive loop in medial frequency region and a capacitive arc in low frequency region. The high frequency capacitive loop, medial frequency inductive loop and low frequency capacitive arc are corresponding to the electron transfer reaction, the formation/adsorption of intermediates and dissolution of corrosion products respectively. All arc of the measured impedance reduced with the increase of the concentration of Ac-, especially HAc. However, the same phenomenon is not notable after reducing pH value by adding HCl. HAc is a stronger proton donor and can be reduced directly by electrochemical reaction firstly. Ac- can't participate in electrochemistry reaction directly, but $Ac^-$ an hydrate easily to create HAc in carbon dioxide saturated environments. HAc is as catalyst in $Co_2$ corrosion. As a result, the corrosion rate was accelerated in the presence of acetate ion even pH value of solution increased.

Detection of N-Acetyltranylcypromine and Glucuronide of Phenyl-Hydroxylated N-Acetyltranlcypromine from Tranylcypromine-Dosed Rat Urine : Pharmacological Implications

  • Kang, Gun-Il;Choi, Hee-Kyung
    • Archives of Pharmacal Research
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    • 제9권2호
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    • pp.99-110
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    • 1986
  • In order to use for metabolic studies of tranylcypromine (TCP), TCP-phenyl-$d_{5}$ was synthesized via the intermediates, 3-benzoylpropionic acid-$d_{5}$ and trans-2-phenylcyclopropanecarboxylic acid-$d_{5}$ -TCP(0.22 mmole/kg) and its deuterated analog were administered s. c. to the rats and GC/MS analyses of the urines led to the detection of N-acetyltranylcypromine (ATCP) and glucuronide conjugate of phenyl-hydroxylated ATCP. MAO activities in rat brain were measured using serotonin as the substrate. In vitro $IC_{50}$ of ATCP was determined to be $10^{-3}M$. The inhibitions by ATCP were not dependent on the preincubation time and were reversed by washing sedimented mitochondrial pellets after the preincubation. In vivo MAO inhibitions at various times of 0.5, 1.5, 3, 6, 12, and 23 hr after the administration of 0.4 mmole/kg (i. p. ) of ATCP were found to be 0.13, 73, 90, 89, and 74 %, respectively. Similarly, the inhibition percents by 0.015 mmole/kg (i. p. ) of TCP were 94, 99, 95, 91, 71 and 49%. The results strongly suggest that deacetylated product of ATCP may account for its in vivo MAO inhibition. The relationship between the metabolism via phenyl-hydroxylation and the in vivo potency of TCP was examined by QSAR study and it was found that groupings discriminating between the compounds with p-substituents and those without them only ensure high correlations, suggesting that ring-hydroxylation which occurs at the para position in most of the compounds is a determining factor to the potency of TCP.

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Biochemical and Ultrastructural Trends in Proteolysis of the $\beta$-subunit of 7S Protein in the Cotyledons During Germination of Soybean Seeds

  • Krishnan, Hari B.
    • 한국작물학회지
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    • 제47권2호
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    • pp.85-94
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    • 2002
  • Antibodies raised against the purified p-subunit of $\beta$-conglycinin were used in immunohistochemical studies to monitor the pattern of $\beta$-conglycinin mobilization in the cotyledons during soybean [Glycine max (L.) Merr.] seed germination. Western blot analysis revealed that the break down of the $\beta$-subunit of $\beta$-conglycinin commenced as early as 2 days after seed imbibition (DAI). Concurrent with the degradation of the $\beta$-subunit of $\beta$-conglycinin, accumulation of 48, 28, and 26 kD proteolytic intermediates was observed from 2 to 6 DAI. Western blot analysis also revealed that the acidic subunit of glycinin was mobilized earlier than the basic subunit. The basic glycinin subunit was subjected to proteolysis within 2 DAI resulting in the appearance of an intermediate product approximately 2 kD smaller than the native basic glycinin subunit. In contrast to the major seed storage proteins, lipoxygenase was subjected to limited proteolysis and was detected even after 8 DAI. The first sign of $\beta$-conglycinin breakdown was observed near the vascular strands and proceeded from the vascular strands towards the epidermis. Protein A-gold localization studies using thin sections of soybean cotyledons and antibodies raised against the $\beta$-subunit of $\beta$-conglycinin revealed intense labeling over protein bodies. A pronounced decrease in the protein A-gold labeling intensity over protein bodies was observed at later stages of seed germination. The protein bodies, which were converted into a large central vacuole by 8 DAI, contained very little 7S protein as evidenced by sparse protein A-gold labeling in the vacuoles.

Functional Identification and Expression of Indole-3-Pyruvate Decarboxylase from Paenibacillus polymyxa E681

  • Phi, Quyet-Tien;Park, Yu-Mi;Ryu, Choong-Min;Park, Seung-Hwan;Ghim, Sa-Youl
    • Journal of Microbiology and Biotechnology
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    • 제18권7호
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    • pp.1235-1244
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    • 2008
  • Indole-3-acetic acid (IAA) is produced commonly by plants and many bacteria, however, little is known about the genetic basis involving the key enzymes of IAA biosynthetic pathways from Bacillus spp. IAA intermediates from the Gram-positive spore-forming bacterium Paenibacillus polymyxa E681 were investigated, which showed the existence of only an indole-3-pyruvic acid (IPA) pathway for IAA biosynthesis from the bacterium. Four open reading frames (ORFs) encoding indole-3-pyruvate decarboxylase-like proteins and putative indole-3-pyruvate decarboxylase (IPDC), a key enzyme in the IPA synthetic pathway, were found on the genome sequence database of P. polymyxa and cloned in Escherichia coli DH5$\alpha$. One of the ORFs, PP2_01257, was assigned as probable indole-3-pyruvate decarboxylase. The ORF consisted of 1,743 nucleotides encoding 581 amino acids with a deduced molecular mass of 63,380 Da. Alignment studies of the deduced amino acid sequence of the ORF with known IPDC sequences revealed conservation of several amino acids in PP2_01257, essential for substrate and cofactor binding. Recombinant protein, gene product of the ORF PP2_01257 from P. polymyxa E681, was expressed in E. coli BL21 (DE3) as a glutathione S-transferase (GST)-fusion protein and purified to homogeneity using affinity chromatography. The molecular mass of the purified enzyme showed about 63 kDa, corresponding closely to the expected molecular mass of IPDC. The indole-3-pyruvate decarboxylase activity of the recombinant protein, detected by HPLC, using IPA substrate in the enzyme reaction confirmed the identity and functionality of the enzyme IPDC from the E681 strain.

4Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octanel-sulfide의 산화반응 중 생성되는 반응성 중간체에 대한 연구 (Investigations of Reactive Intermediate formed in the oxidation of 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2] octane 1-sulfide)

  • 김정한
    • Applied Biological Chemistry
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    • 제39권3호
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    • pp.227-234
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    • 1996
  • 4-Methyl-2,6,7-trioxa-1-phospbicycle[2,2,2]octane 1-sulfide (BPS)와 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octance 1-oxide (BPO) 및 관련 단고리화합물을 합성하였고 반응성 중간체와 반응기작을 알아보기 위하여 BPS를 chloroform 및 methanol중에서 MCPBA로 산화시켰다. Chloroform에서는 BPO만이 생성되었고 methanol중에서는 두고리 구조가 열려서 만들어진 반응성 중간체가 methanol을 인산화하여 생성된 이성질체의 단고리화합물이 관찰 되었으며 또한 소량의 BPO도 생성되었다. 인산화 능력을 소유한 반응성 중간체를 여러 가지 기기분석을 동원하여 연구한 결과 그 구조는 단고리 methyl sulfenyl ester로 제안하였다.

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회분식 실험 Substrate/Microorganisms 비에 따른 종속영양미생물의 특이거동 연구 (Abnormal Behavior of Ordinary Heterotrophic Organism Active Biomass at Different Substrate/Microorganisms Ratios in Batch Test)

  • 이병준;;;민경석
    • 한국물환경학회지
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    • 제20권3호
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    • pp.197-205
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    • 2004
  • Batch test methods have developed for a long time to measure kinetic and stoichiometric parameters which are required to perform steady state design and mathematical modelling of activated sludge processes. However, at various So/Xo ratios, abnormal behaviors of ordinary heterotrophic organism in batch tests have been reported in many researches. Thus, in this research, abnormal behaviors of heterotrophs in batch tests were investigated at various So/Xo conditions by measuring and interpreting oxygen utilization rate. As So/Xo ratio increased, the calculated values of maximum specific growth rates, ${\mu}_{H,max}$ and $K_{MP,max}$, increased. However, at a certain point of So/Xo (around 10mgCOD/mgMLAVSS), ${\mu}_{H,max}$ and $K_{MP,max}$ values started to decrease. According to this observation, three prominent behaviours of heterotrophs were identified at various So/Xo conditions. (1) At low So/Xo region (below 5 mgCOD/mgMLAVSS), the oxygen utilization rate of heterotrophs in batch tests were almost stable and consequently yielded lower maximum specific growth rate. (2) At high So/Xo region (up to 5~10 mgCOD/mgMLAVSS), oxygen utilization rate incresed sharply with time and indicated more upward curvature than the predicted OUR with conventional activated sludge model, which consists of single hetetrotrophs group. Thus, in this region, competition model of two organisms, fast-grower and slow-grower, seemed to be appropriate. (3) At extremely high So/Xo region (over 10mgCOD/mgMLAVSS), significant oxygen utilization rate was still observed even after depletion of readily biodegradable COD. This might be caused by retarded utilization of intermediates which were generated by self inhibition mechanism in the process of RBCOD uptake.

클라우드 사용자 요구사항 기반으로 클라우드 서비스 중개를 위한 가상 클라우드 뱅크 아키텍처 (Architecture of Virtual Cloud Bank for Mediating Cloud Services based on Cloud User Requirements)

  • 박준석;안영민;염근혁
    • 정보과학회 논문지
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    • 제42권9호
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    • pp.1090-1099
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    • 2015
  • 클라우드 컴퓨팅 패러다임의 등장에 따라 다수의 클라우드 서비스와 클라우드 사용자를 연계해 주는 CSB(Cloud Service Brokerage) 라는 개념이 제시되었다. CSB 에 등록되어 비슷한 기능을 제공하는 클라우드 서비스들은 제공자마다 성능, 가격 등에 차이가 있으므로, 클라우드 사용자가 클라우드 서비스를 사용하기 위해 적합한 서비스를 찾기 어렵다. 따라서 다수의 클라우드 서비스 중에서 클라우드 사용자의 요구사항에 가장 적합한 클라우드 서비스를 찾아주는 방법을 CSB 에서 핵심적으로 고려해야 한다. 본 논문은 클라우드 사용자의 요구사항을 수집하고 분석하는 방법과 다양한 클라우드 서비스를 명세하는 SAM을 포함하는 CSB 로써 가상 클라우드 뱅크 아키텍처를 제시한다. 본 논문에서 제시한 가상 클라우드 뱅크 아키텍처는 클라우드 사용자의 요구사항에 적합한 클라우드 서비스 제공을 위한 CSB의 참조아키텍처로 활용할 수 있다.