• Title/Summary/Keyword: intermediates

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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.
    • Journal of the Korean Electrochemical Society
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    • v.7 no.4
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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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    • v.35 no.2
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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.

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

  • Chung, Young-Min
    • Clean Technology
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    • v.20 no.2
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    • pp.116-122
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    • 2014
  • Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic performance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

$Co_2$ 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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    • v.6 no.5
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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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    • v.9 no.2
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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.
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.47 no.2
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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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    • v.18 no.7
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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.

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

  • Kim, Jeong-Han
    • Applied Biological Chemistry
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    • v.39 no.3
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    • pp.227-234
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    • 1996
  • 4-Methyl-2,6,7-trioxa-1-phosphabicyclo [2,2,2] octane 1-sulfide (BPS), 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2] octane 1-oxide (BPO) and related monocyclic methylphosphates were prepared and the oxidation of BPS with MCPBA in chlorofrom or methanol was carried out to investigate the formation of reactive intermediates and reaction mechanism. BPO was the only product in chloroform while in methanol isomeric monocyclic methylphosphates were formed through opening of bicylic structure with subsequent phosphorylation of methanol by reactive intermediate formed in reaction. Formation of little amount of BPO was also observed. The structure of phosphorylating intermediate was probed with various spectroscopic methods and monocyclic methyl sulfenyl ester was suggested as a possible structure.

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

  • Lee, Byung-Joon;Wentzel, M.C.;Ekama, G.A.;Min, Kyung-Sok
    • Journal of Korean Society on Water Environment
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    • v.20 no.3
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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.

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

  • Park, Joonseok;An, Youngmin;Yeom, Keunhyuk
    • Journal of KIISE
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    • v.42 no.9
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    • pp.1090-1099
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    • 2015
  • The concept of Cloud Service Brokerage (CSB) has been introduced as a result of the expansion of the cloud-computing paradigm. Cloud services that provide similar functionality are registered with a CSB. A CSB intermediates cloud services between cloud users and providers. However, there are differences in the price and performance offered by each of the cloud providers. Thus, cloud users have difficulty in finding suitable services to use. Therefore, a CSB is required in order to provide an approach for cloud services to fulfill the requirements of cloud users. In this paper, we propose a virtual cloud bank architecture that includes both a Service Analysis Model (SAM) that can be used to specify and analyze various cloud services and a requirement analysis method that can be used to collect and analyze the cloud user requirements. The VCB architecture that is herein proposed can be used as a reference architecture to provide user-centric cloud services.