• Title/Summary/Keyword: Rate Determining Step

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Recent Advances in Cancer Diagnosis: On an Overview of Diagnostic Cytopathologic Modalities and Ancillary Techniques (세포병리학적 기초에 의한 암진단의 발전: 진단방법과 보조기법)

  • Kim, Ki-Tai;Ham, Eui-Keun
    • The Korean Journal of Cytopathology
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    • v.7 no.1
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    • pp.1-11
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    • 1996
  • From the concepts of cellular pathology and of exfoliative cytology, as elucidated by Virchow and Papanicolaou respectively in the late 19th and early 20th century, have evolved the primary methods for the diagnosis of cancer today. From Papanicolaou's concept of exfoliative cytology developed fine needle aspiration biopsy in the early 1960's, this has become a major diagnostic procedure and has contributed to a significant reduction in open biopsies and, therefore, to medical cost-effectiveness immunobiochemical techniques provided us with a supplement to cancer diagnosis in the 1980's. The immunoperoxidase method, using monoclonal antibodies, is applied primarily as an ancillary measure to elucidate the nature of cancers The availability of specific monoclonal antibodies has greatly facilitated the identification of cell products or surface markers. For example, antibodies directed against intermediate filaments have proved to be of value in determining the histogenesis oi poorly differentiated neoplasms. Tumor markers may serve as biochemical indicators of the presence of a neoplasm. They can be detected In plasma and other body fluids. Their concentration can be applied as a diagnostic test, for monitoring the clinical course of known cancer, and as a screening measure to detect certain cancers in a population at risk. Flow cytometry is a useful tool for distinguishing several cell characteristics, such as the immunophenotype of leukemia-lymphoma cells, the DNA content of neoplastic cells, and cell proliferation rate. Molecular biologic techniques provided a giant step for the management of cancer patients encompassing diagnosis, prognostic evaluation, and therapy. Nucleic acid hybridization techniques are utilized as Southern, Northern, and dot blots and in situ hybridization. Molecular biology and its techniques may bring a blight new horizon for understanding cancer biology and in designing therapy on the basis of gene manipulation.

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A Study on the Hydrolysis of Sarin and Soman by Merrifield-Type Diaminatedpolystyrene-Cu (II) Heterogeneous Polymers (Merrifield-Type Diaminatedpolystyrene-Cu (II) 불균일 촉매에 의한 Sarin과 Soman 분해반응 연구)

  • 정우영;계영식
    • Journal of the Korea Institute of Military Science and Technology
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    • v.3 no.1
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    • pp.164-175
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    • 2000
  • Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

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Kinetics and Mechanism of the Oxidation of Sulfur Dioxide on Nickel Oxide-${\alpha}$-Ferric Oxide System (산화니켈-${\alpha}$ 형 산화철 상에서 이산화황의 산화 반응메카니즘)

  • Kyu Yong Lee;Yong Rok Kim;Sung Han Lee
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.183-188
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    • 1983
  • The catalytic oxidation of $SO_2$ has been investigated in the presence of vacuum-activated 10 mol % Ni-doped ${\alpha}-Fe_2O_3$ under various partial pressures of $SO_2\;and\;O_2$ at temperatures from 320 to $440{\circ}C$. Over the temperature range $320{\sim}440{\circ}C$, the activation energy is 13.8 $kcal{\cdot}mol^{-1}$. The oxidation rates have been correlated with 1.5 order kinetics; first order with respect to $SO_2$ and 0.5 order with respect to $O_2$. From the kinetic data and conductivity measurements, the adsorption, oxidation mechanism of $SO_2$ and the defect structure of vacuum-activated 10 mol % Ni-doped {\alpha}-Fe_2O_3$ are suggested. $O_2\;and\;SO_2$ appear to be adsorbed essentially as ionic species. Two surface sites, probably an $O^{2-}$ lattice and an oxygen vacancy which is induced by Ni-doping, might be required to adsorb $SO_2\;and\;O_2$. The conductivity measurements and kinetic data indicate that the adsorption process of $SO_2\;{(SO_2+O^{2-}}_{(latt)}{\rightleftharpoons}{{SO_3}^-}_{(ads)}+e')$ is the rate-determining step.

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A Basic Study on the Production of $Sm_{2}Fe_{17}N_{x}$ System Rare Earth Permanent Magnet by the Reduction and Diffusion(I) - Production of Alloy Powder of $Sm_{2}Fe_{17}$ Intermetallic Compound - (환원.확산법에 의한 $Sm_{2}Fe_{17}N_{x}$ 계 희토류 영구자석의 제조에 관한 기초연구(제 1보) -$Sm_{2}Fe_{17}$금속간화합물 합금분말의 제조-)

  • Song, Chang-Bin;Choo, Tong-Rae
    • Korean Journal of Materials Research
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    • v.8 no.8
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    • pp.720-725
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    • 1998
  • As a basic study on the production of $Sm_{2}Fe_{17}N_{x}$ system rare earth permanent magnet by the reduction and diffusion(R- D) process, firstly the reduction reaction of $Sm_2O_3$ by metallic Ca and diffusion of Sm into Fe powder was investigated for the production the $Sm_{2}Fe_{17}$intermetallic compound. We concluded that the former case was very rapidly completed under the high temperature greater than 100$0^{\circ}C$ and the latter case of completion of diffusion reaction of Sm into the center of Fe powder(perfect homogenization condition) was required through 3h R- D reaction at 110$0^{\circ}C$ and identified as a rate determining step(RDS) on the whole reaction. Though $SmFe_2,SmFe_3$, and $Sm_{2}Fe_{17}$phases in the growth of phases of intermetallic compound in the Sm - Fe binary system were obseved below 100$0^{\circ}C$, but only $Sm_{2}Fe_{17}$phase was observed at lIOO$^{\circ}C$. Oxygen and Ca contents of the final sample in this work were 0.72wt% and O. 11 wt% respectively.

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Slit Ventricle Syndrome in Children : Clinical Presentation and Treatment (소아에서 틈새뇌실 증후군 : 임상 양상 및 치료)

  • Shin, Beom-Sik;Yang, Kook-Hee;Kim, Dong-Seok;Choi, Joong-Uhn
    • Journal of Korean Neurosurgical Society
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    • v.30 no.sup2
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    • pp.309-315
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    • 2001
  • The term slit ventricle syndrome(SVS) refers to an episodic occurrence of headache, vomiting, and possibly some degree of impaired consciousness in shunted hydrocephalic children in whom slit-like ventricles are seen on CT scan or MRI. Authors present 6 cases with SVS who were treated at our institute for last 10 years. From 1986 to 1996, 821 patients underwent shunt surgery for hydrocephalus. The etiology of hydrocephalus included brain tumor(140 patients), post-hemorrhagic(62 patients), idiopathic normotensive hydrocephalus(64 patients), post-meningitic( 58 patients), post-traumatic(54 patients), congenital(48 patients), neurocysticercosis(31 patients), and unknown etiology(364 patients). During the mean follow-up duration of 68 months, 232 shunt revisions were performed by a revision rate of 1.28 per patient. The incidence of SVS was 0.7%(6 patients). Most of them have been operated on in infancy. Time interval from the first operation to the development of slit-ventricle syndrome ranged from 4 to 8 years, the mean was 6 years. Shuntogram showed patent shunt in all patients. Two patients with less severe clinical symptoms improved with conservative treatment. These patients were not measured ICP because of good hospital course. One patient showed high ICP and needed only revision with same pressure valve as previous shunt. Low ICP was noted in 3 patients. Pressure augmentation using an anti-siphon device(ASD) or upgrading valve system were necessary in these patients. The authors stress that determining type of SVS is the first step in treatment planning and that the best treatment is a strategy aimed at resolving the specific type of SVS responsible for the symptoms.

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Optimal Period by Calculating and Appling Correction Factor based on Setting of Non-Working Days of Construction Projects (건설공사의 작업불능일 기준설정에 의한 보정계수 계산 및 적용을 통한 최적공기 산정)

  • Lee, Pil-Yoon;Lee, Seong-Won;Byun, Yo-Seph;Cho, Choong-Yeun;Lee, Min-jae
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.12
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    • pp.669-676
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    • 2018
  • Schedule management in construction work is an important step for determining the construction period. On the other hand, there is a difference between the planned schedule and execution schedule because the estimation and calculation of Non-Working days, in which possible at the design stage is not performed properly. This paper proposes a method for estimating the working days by analyzing characteristics of the major work type and estimating the Non-Working days reflecting the Chuseok and New Year Holidays, which is the closest method to the actual work in the schedule planning. By applying the correction factor of the existing method and the improved method for the same construction in the same site, improved method was reduced by 22 days (9.1%) based on the actual working days. The importance of schedule management was confirmed as an example by comparing the data before and after the application of the standard (plan). These results show that the schedule delays, which are caused by the inconsistency between actual working days calculation that had been practiced conventionally and the working days on the schedule table, can be prevented. In addition, it will help to establish a schedule plan that is closer to reality.

A Kinetic Study on the Nucleophilic Substitution Reaction of 2,4-dinitrophenyl 5-substituted-2-furoates Under R2NH/R2NH2+ in 20 mol% DMSO(aq). Effects of Nonleaving Group and Leaving Group on the Reaction Mechanism (R2NH/R2NH2+-20 mol% DMSO(aq)의 조건에서 2,4-dinitrophenyl 5-substituted-2-furoates의 아실 이동반응에 대한 반응속도론적 연구. 반응 메커니즘에 미치는 비이탈기와 이탈기의 효과)

  • Sang Yong Pyun;Kyu Cheol Paik;Man So Han;Bong Rae Cho
    • Journal of the Korean Chemical Society
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    • v.67 no.3
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    • pp.191-198
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    • 2023
  • Acyl transfer reactions of 2,4-dinitrophenyl-5-substituted-2-furoates (1a-d) promoted by R2NH/R2NH2+ in 20mol% DMSO(aq) have been studied kinetically. The reactions are second-order and exhibit downward curves of the Brönsted plots with pKa0 = 9.5, β1 = 0.23-0.35 and β2 = 0.88-0.99. The k1 values increased with a stronger nucleophile and as the electron-withdrawing ability of the 5-furyl substituent increases. In contrast, the k2/k-1 values were nearly idential regardless of the 5-furyl substituents. From these results, a stepwise mechanism with a change in the rate-determining step(RDS) is proposed.

Formation and Dissociation Kinetics of Zinc(II) Complexes of Tetraaza-Crown-Alkanoic Acids (Zinc(Ⅱ) Tetraaza-Crown-Allkanoic Acids 착물의 형성 및 해리 반응속도론)

  • Choi, Ki Young;Kim, Dong Won;Kim, Chang Suk;Park, Byung Bin;Choi, Suk Nam;Hong, Choon Pyo;Ryu, Hae Il
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.403-409
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    • 2000
  • The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

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Analysis and Prediction of Sewage Components of Urban Wastewater Treatment Plant Using Neural Network (대도시 하수종말처리장 유입 하수의 성상 평가와 인공신경망을 이용한 구성성분 농도 예측)

  • Jeong, Hyeong-Seok;Lee, Sang-Hyung;Shin, Hang-Sik;Song, Eui-Yeol
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.3
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    • pp.308-315
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    • 2006
  • Since sewage characteristics are the most important factors that can affect the biological reactions in wastewater treatment plants, a detailed understanding on the characteristics and on-line measurement techniques of the influent sewage would play an important role in determining the appropriate control strategies. In this study, samples were taken at two hour intervals during 51 days from $1^{st}$ October to $21^{st}$ November 2005 from the influent gate of sewage treatment plant. Then the characteristics of sewage were investigated. It was found that the daily values of flow rate and concentrations of sewage components showed a defined profile. The highest and lowest peak values were observed during $11:00{\sim}13:00$ hours and $05:00{\sim}07:00$ hours, respectively. Also, it was shown that the concentrations of sewage components were strongly correlated with the absorbance measured at 300 nm of UV. Therefore, the objective of the paper is to develop on-line estimation technique of the concentration of each component in the sewage using accumulated profiles of sewage, absorbance, and flow rate which can be measured in real time. As a first step, regression analysis was performed using the absorbance and component concentration data. Then a neural network trained with the input of influent flow rate, absorbance, and inflow duration was used. Both methods showed remarkable accuracy in predicting the resulting concentrations of the individual components of the sewage. In case of using the neural network, the predicted value md of the measurement were 19.3 and 14.4 for TSS, 26.7 and 25.1 for TCOD, 5.4 and 4.1 for TN, and for TP, 0.45 to 0.39, respectively.

An Integrated Model based on Genetic Algorithms for Implementing Cost-Effective Intelligent Intrusion Detection Systems (비용효율적 지능형 침입탐지시스템 구현을 위한 유전자 알고리즘 기반 통합 모형)

  • Lee, Hyeon-Uk;Kim, Ji-Hun;Ahn, Hyun-Chul
    • Journal of Intelligence and Information Systems
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    • v.18 no.1
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    • pp.125-141
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    • 2012
  • These days, the malicious attacks and hacks on the networked systems are dramatically increasing, and the patterns of them are changing rapidly. Consequently, it becomes more important to appropriately handle these malicious attacks and hacks, and there exist sufficient interests and demand in effective network security systems just like intrusion detection systems. Intrusion detection systems are the network security systems for detecting, identifying and responding to unauthorized or abnormal activities appropriately. Conventional intrusion detection systems have generally been designed using the experts' implicit knowledge on the network intrusions or the hackers' abnormal behaviors. However, they cannot handle new or unknown patterns of the network attacks, although they perform very well under the normal situation. As a result, recent studies on intrusion detection systems use artificial intelligence techniques, which can proactively respond to the unknown threats. For a long time, researchers have adopted and tested various kinds of artificial intelligence techniques such as artificial neural networks, decision trees, and support vector machines to detect intrusions on the network. However, most of them have just applied these techniques singularly, even though combining the techniques may lead to better detection. With this reason, we propose a new integrated model for intrusion detection. Our model is designed to combine prediction results of four different binary classification models-logistic regression (LOGIT), decision trees (DT), artificial neural networks (ANN), and support vector machines (SVM), which may be complementary to each other. As a tool for finding optimal combining weights, genetic algorithms (GA) are used. Our proposed model is designed to be built in two steps. At the first step, the optimal integration model whose prediction error (i.e. erroneous classification rate) is the least is generated. After that, in the second step, it explores the optimal classification threshold for determining intrusions, which minimizes the total misclassification cost. To calculate the total misclassification cost of intrusion detection system, we need to understand its asymmetric error cost scheme. Generally, there are two common forms of errors in intrusion detection. The first error type is the False-Positive Error (FPE). In the case of FPE, the wrong judgment on it may result in the unnecessary fixation. The second error type is the False-Negative Error (FNE) that mainly misjudges the malware of the program as normal. Compared to FPE, FNE is more fatal. Thus, total misclassification cost is more affected by FNE rather than FPE. To validate the practical applicability of our model, we applied it to the real-world dataset for network intrusion detection. The experimental dataset was collected from the IDS sensor of an official institution in Korea from January to June 2010. We collected 15,000 log data in total, and selected 10,000 samples from them by using random sampling method. Also, we compared the results from our model with the results from single techniques to confirm the superiority of the proposed model. LOGIT and DT was experimented using PASW Statistics v18.0, and ANN was experimented using Neuroshell R4.0. For SVM, LIBSVM v2.90-a freeware for training SVM classifier-was used. Empirical results showed that our proposed model based on GA outperformed all the other comparative models in detecting network intrusions from the accuracy perspective. They also showed that the proposed model outperformed all the other comparative models in the total misclassification cost perspective. Consequently, it is expected that our study may contribute to build cost-effective intelligent intrusion detection systems.