• Title/Summary/Keyword: Steric Effect

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Synthesis of Sulfonamide Derivatives as New Herbicidal Compounds and Studies on Biological Activity (새로운 Sulfonamide 유도체의 합성과 Acetolactate Synthase (ALS) 저해)

  • Chae, Jong-Kun;Lee, Jae-Seob;Choi, Jung-Do;Shin, Jung-Hyu
    • Applied Biological Chemistry
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    • v.41 no.1
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    • pp.99-103
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    • 1998
  • Triazolopyrimidine sulfonanilide (TP) derivative is one of excellent herbicide compounds. We have synthesized three classes of a new sulfonamide derivative (TPP) as Acetolactate synthase (ALS) inhibitors, in which the benzene ring in TP skeleton was converted to substituted pyrimidyl ring and examined their inhibitory activities on barley for ALS. $I_{50}$ values of the inhibitors ranged from 0.005 to 2 mM. Comparing the $I_{50}$ value of each class of TPP derivatives, the substituents in pyrimidine and triazolopyrimidine ring were found to affect the degree of ALS inhibition. TPP with substituted methyl group in pyrimidine ring showed higher inhibitory activity than that with methoxy group, while the substitution of the cyclopentano group in triazolopyrimidine ring gave very large inhibitory activity than that of methyl group. The present study established that variation of the electron density by substitution at heterocyclic ring is a very important factor for ALS inhibition, but showed no dependence on steric effect by substituents.

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A Preparation and Characteristics of Functional rchitecture Materials Made frm Non-metallic Minerals (비금속광물 분체의 기능성 건축소재화 특성)

  • 김병곤;최상근;박종력;전호석
    • Journal of the Korean Ceramic Society
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    • v.40 no.8
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    • pp.811-817
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    • 2003
  • Recently, application fields of non-metallic minerals by utilizing their structure properties are broadening. Especially, layered minerals have not only excellent shielding or covering ability but also absorbing and storing characteristics of chemical elements between a layers. We considered about the above mentioned characteristics and added functional substances onto their surfaces for the preparation of new environmentally friendly functional materials. In this study, natural graphite and sericite were mainly used to produce for the new environmentally friendly functional building materials. Graphite surfaces were modified with a surfactant (Alkyl Benzyle Demethyle Ammonium Chloride) for anti-bacillus and penicillium. Surface modification mechanism are that primary adsorption by differential zeta potential between graphite and ABDM and secondary adsorption by interaction between surfactant chains take place. Surfactant layers were fully formed and it was expected up to 99.7% up the efficiency of anti-bacillus and penicillium. Also the prepared functional samples have a effect to improve a various efficiency such as electromagnetic wave shield(up to 95%), deodorization(up to 80%), heat storage(5%) etc.

A Study on the Detergency Performance of Zeolite A in the Detergent Solution (세제용액 중에서 Zeolite A의 세정성능에 관한 연구)

  • Kang, Yun-Seog;Kim, Hyun-Chang;Nam, Ki-Dae
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.624-630
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    • 1997
  • Zeolite A helps an increase of detergency performance according to showing the ion exchange effect for polyvalant ions and it's detergency performance could be calculated quantitatively by using the disperse stabilization theory because it is water-insoluble material and is as colloid particles in aqueous solution. In this study, zeta potential of carbon black, cellulose, and Zeolite A were measured in each inorganic salt solutions and applied to the theory of Heterocoagulation in order to evaluate the detergency performance of Zeolite A about the particulate soil at the view point of interaction potential energy. Zeolite A was shown help an increase of detergency performance according to the increasing of the steric repulsion between Zeolite A and cellulose in $Na2CO_3$ solution and the decrease of re-deposition of carbon black on the fabric by rapid coagulation with carbon black in $Na_2SO_4$ solution.

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Separation of Optical Isomers of DNS-Amino Acids in High-Performance Liquid Chromatography (고성능 액체크로마토 그래피에 의한 Dansyl-아미노산 광학이성질체의 분리)

  • Sun Haing Lee;Tae Sub O;Kyung Sug Park
    • Journal of the Korean Chemical Society
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    • v.30 no.2
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    • pp.216-223
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    • 1986
  • Separation of optical isomers of DNS derivatized amino acids by a reversed-phase high-performance liquid chromatography has been studied by adding a complex of an optically active amino acid (L-arginine) with the metal ion (Cu(II), Zn(II), Cd(II), Ni(II)) to the mobile phase. The separations are affected by the concentrations of acetonitrile, chelate and buffer. They are also affected by the pH and the kinds of metal and buffer. A separation mechanism, which is based on steric effect of the ligand exchange reaction for the formation of ternary complexes by the D,L-DNS-amino acids and the chiral additive associated with the stationary phase, is proposed to interpret the elution behaviors of D, L-dansyl-amino acids.

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Determination of Reactivity by MO Theory (XXXIV). MINDO/3 Theoretical Studies on Sigmatropic Hydrogen Rearrangements (1) : Systems with Central Carbon Atom (분자궤도론에 의한 반응성 결정 (제34보). 수소 시그마 결합 자리옮김 반응에 대한 MINDO/3 이론연구 (1) : 중앙탄소원자를 가진 계)

  • Cho, Jeoung-Ki;Lee, Ik-Choon;Oh, Hyuck-Keun;Cho, In-Ho
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.217-230
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    • 1984
  • The MINDO/3 method was used in determination of transition states and activation barriers for various 1,2-, 1,3- and 1,5-sigmatropic hydrogen rearrangements involving systems with central carbon atom. It was found that, besides the consideration of orbital symmetry, steric effect, aromaticity, and orbital interactions were found to dictate the stability of the transition state. For systems with hetero atoms, lone pair orbitals tend to ease orbital distortion required at the transition state by participating in hydrogen transfer process and were found to lower the activation barrier accordingly. Comparison of the relative barrier heights with those obtained by using more sophisticated ab initio MO calculations showed that the MINDO/3 results give qualitatively the same tendency of the relative order of the activation barriers.

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Determination of Reactivities by MO Theory (ⅩⅡ). Nucleophilic Substitution Reactions of N-Acetylpiperidone (MO 理論에 依한 反應性의 決定 (第12報). N-아세틸피페리돈의 親核性 置換反應)

  • Lee Ik Choon;Kim Shi Choon;Lee Suk Kee;Park Dong Whan;Jeon Young Gu
    • Journal of the Korean Chemical Society
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    • v.22 no.6
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    • pp.396-402
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    • 1978
  • MO theoretical studies on the conformation and the acid-catalyzed nucleophilic substitution of N-acetylpyperidone were carried out by EHT, CNDO/2 and the orbital mixing analytical methods. MO calculations show that the most preferred conformation is the half-chair, cis-trans form and the protonation occurs most readily on the acetyl carbonyl oxygen. These results were interpreted in terms of conjugative, electrostatic and steric effect. From orbital mixing analysis, we found also that the reactivity of protonated carbonyl carbon is greatly enhanced due to increase in positive charge (for charge controlled reaction) of the carbonyl carbon atom. Accordingly, the acetyl cleavage will be preferred in the nucleophilic substitution (acid-catalyzed hydrolysis) to the ring cleavage.

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Separation of Bacteria Using Capillary Electrophoresis (모세관 전기영동을 이용한 박테리아의 분리)

  • Moon, Byoung-Geoun;Choi, Kyu-Seong;Lee, Sang-Chun;Kim, Yong-Seong
    • Journal of the Korean Chemical Society
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    • v.48 no.2
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    • pp.144-150
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    • 2004
  • Various experimental factors that affect the separation of bacteria were investigated using capillary electrophoresis. At different buffer concentrations, gram-positive bacteria and gram-negative bacteria showed somewhat different migration behavior under high electric filed. The separation efficiency was also investigated as a function of concentration of bacterium injected into the capillary. In order to separate bacteria as the difference of size and shape, water soluble polymers such as poly(ethylene)oxide (PEO), polyvinylpyirrolidone (PVP), and dextran were studied. PEO, which is more flexible and has lower steric hinderance, showed the best separation efficiency. The mixed bacteria sample of Micrococcus lysodeikticus as gram-positive bacteria and Aerobacter aerogenes as gram-negative bacteria were successfully analyzed with PEO.

Effect of External and Intramolecular Nucleophiles on Nature of Products of Carboxypeptidase A-Catalyzed Hydrolysis of Esters. Attempted Trapping of Acyl-Enzyme Intermediate (카르복시펩티다제A의 에스테르 가수분해 반응생성물의 종류에 대한 외부 및 분자내 친핵체의 영향. 아실-효소중간체의 포획시도)

  • Junghun Suh;Emil Thomas Kaiser
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.164-172
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    • 1978
  • Carboxypeptidase A-catalyzed hydrolysis of ester substrates was carried out at room temperature in the presence of a number of external reagents. If the acyl-enzyme intermediate, an anhydride, is attacked by the external reagents, products formed by trapping at the acyl portion or at the enzyme portion of the anhydride group can be obtained. Examination of the uv/vis spectral properties of the reaction products and of changes in enzyme activity indicated that such trapping reactions did not occur. Also performed was evaluation of enzymatic rate parameters for the the hydrolysis of O-(o-hydroxyphenylacetyl)-L-${\beta}$-phenyllactate. Detection of 2-coumaranone possibly formed by attack of the o-hydroxy group as an intramolecular trapping group at the acyl-enzyme intermediate was tried, but no evidences for the intramolecular trapping reaction were obtained. Failure to trap the intermediate was discussed in terms of steric hindrance imposed on the approach of the trapping reagents to the anhydride group of the acyl-enzyme intermediate and of the fast enzymatic breakdown of the intermediate.

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Kinetics and Mechanism of Hydrolysis of Insecticidal $O,O-diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothiate\;(Volaton^{\circledR})$ (살충성 $O,O-Diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothioate\;(Volaton^{\circledR})$의 가수분해 반응메카니즘)

  • Sung, Nack-Do;Kim, Hyune-Yi;Park, Cheon-Kyu
    • Applied Biological Chemistry
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    • v.37 no.2
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    • pp.124-129
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    • 1994
  • The rate of hydrolysis of insecticidal $O,O-diethyl-{\alpha}-cyanobenzylideneamino-oxyphosphorothioate\;(Volaton^{\circledR})$ has been studied in 25% (v/v) aqueous dioxane. On the basis of solvent effect (pH 6.0; m=0.21, n=1.55, pH 12.0; m=0.42, n=3.14 & $|m|{\ll}|l|$), general base catalysis, hydrolysis product analysis, calculation of molecular orbital (MO) and rate equation, it may be concluded that the hydrolysis of Volaton proceeds through the $A_{AC}2$ mechanism via trigonal bipyramidal $(sp^3d^2)$ intermediate below pH 7.0, while above pH 9.0 the hydrolysis proceeds through the $B_{AC}2$ mechanism. Hydrolysis reactivity of Volaton depends on positive charge strength $(p{\gg}{\alpha}C_2)$ rather than steric hindrance. In the range between pH 7.0 and pH 9.0, these two reactions occur competitively.

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Effect of Poly(vinyl alcohol) and Poly(vinyl alcohol) Mono Thiol on the Stability Properties of Poly(vinyl acetate) Latex (폴리비닐알코올과 폴리비닐알코올모노티올이 폴리초산비닐 라텍스의 안정성에 미치는 영향)

  • 이서용;박이순
    • Polymer(Korea)
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    • v.24 no.5
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    • pp.579-588
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    • 2000
  • The effects of protective colloids on the colloid stability of poly(vinyl acetate) (PVAc) latex was investigated. The stability of PVAc latex in reactive poly(vinyl alcohol) mono thiol (PVALT) (DP=1080) having 78.4% saponification value was better than poly (vinyl alcohol)(PVA) (DP=1100) having 81.6% saponification value. The colloidal stability of PVAc latex particles improved drastically with increase of the reactive PVALT. The particle surface morphology of PVAc latex was examined by transmission electron microscopy (TEM). It was shown that particle size of 1ha latexes decreased with increasing reactive PVALT concentration. Therefore, the stabilities of latex for reactive PVALT protective colloid was superior to that of PVA ones. This result is due to the introduction of many thiol groups that induce chemical bonds at PVAc latexes surface, so that the formation of PVALT-b-PVAc block copolymer via the reaction of PVAc with reactive PVALT. In addition, zeta potential of the PVAc latexes decreased with increasing sodium carbonate concentration.

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