• Title/Summary/Keyword: Steric Effect

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Anticancer Mechanisms of 3-Heptylamino-6-Allylthiopyridazine and 3-Dipentylamino-6-Allylthiopyridazine in Human Colon Carcinoma RKO Cells (RKO 대장암세포에서 3-헵틸아미노-6-알릴티오피리다진과 3-디펜틸아미노-6-알릴티오피리다진의 항암기전)

  • Lim, Hyun Kyung;Kwon, Yumi;Song, Jiyun;Kim, Kyoung Mee;Kim, Chaewon;Park, Myung-Sook;Jung, Joohee
    • YAKHAK HOEJI
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    • v.60 no.3
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    • pp.101-106
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    • 2016
  • Allylthiopyridazine derivatives were synthesized and evaluated for anti-proliferative activities in the previous study. In this study, selected two allylthiopyridazine derivatives (compound I, 3-heptylamino-6-allylthiopyridazine and compound II, 3-dipentylamino-6-allylthiopyridazine) were assessed for cytotoxicity and chronic proliferation in human colon carcinoma RKO cells. Two derivatives dose-dependently inhibited cell viability and proliferation. To elucidate the anticancer mechanism of two derivatives, we investigated the expression level of apoptosis-related proteins in RKO cells. Compound I induced the activation of JNK and expression of p53 and p21. On the other hand, compound II showed no change of p53 level. Interestingly, compound II inhibited the nuclear translocation of NF-${\kappa}B$. This result suggested that compound II suppressed cell proliferation. These different mechanisms of these compounds might have occurred through different steric conformation.

Ring-Opening Polymerization of $\varepsilon$-Caprolactone and Cyclohexene Oxide Initiated by Aluminum $\beta$-Ketoamino Complexes: Steric and Electronic Effect of 3-Position Substituents of the Ligands

  • Liu, Binyuan;Li, Haiqing;Ha, Chang-Sik;Kim, Il;Yan, Weidong
    • Macromolecular Research
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    • v.16 no.5
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    • pp.441-445
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    • 2008
  • A series of aluminum complexes supported by $\beta$-ketoamino, ligand-bearing, 3-position substituents $LAlEt_2$ ($L=CH_3C(O)C(Cl)=C(CH_3)NAr\;(L_1)$, $L=CH_3C(O)C(H)=C(CH_3)NAr\;(L_2)$, $L=CH_3C(O)C(Ph)=C(CH_3)NAr\;(L_3)$, and $L=CH_3C(O)C(Me)=C(CH_3)NAr\;(L_4)$, $Ar=2,6-^iPr_2C6H_3$) were synthesized in situ and employed in the ring-opening polymerization (ROP) of $\varepsilon$-caprolactone ($\varepsilon$-CL) and cyclohexene oxide (CHO). The 3-position substituents on the $\beta$-ketoamino ligand backbone of the aluminum complexes influenced the catalyst activity remarkably for both ROP of $\varepsilon$-CL and CHO. Aluminum $\beta$-ketoamino complexes displayed different catalytic behavior in ROP of $\varepsilon$-CL and CHO. The order of the catalytic activity of $LAlEt_2$ was $L_1AlEt_2$>$L_2AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$ for ROP of $\varepsilon$-CL, being opposite to the electron-donating ability of the 3-position substituents on the $\beta$-ketoamino ligand, while the order of the catalytic activity for ROP of CHO was $L_1AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$>$L_2AlEt_2$. The effects of reaction temperature and time on the ROP were also investigated for both $\varepsilon$-CL and CHO.

Kinetics Studies on Nucleophilic Reactions of Methanesulfonyl Chloride with Substituted Aniline in Methanol (메탄올 속에서 치환아닐린과 염화메탄술포닐의 친핵성반응의 속도론적 연구)

  • Lee Suk-Kee
    • Journal of the Korean Chemical Society
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    • v.19 no.3
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    • pp.156-162
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    • 1975
  • Rates of reactions of methanesulfonyl chloride with various substituted anilines have been measured in methanol. Substituent effects in aniline are found to be linearly correlated with pKa(Bronsted relation with ${\beta}$ = 0.84) and ${\rho}$(Hammett equation with ${\rho}$ = -2.46) respectively. The results are interpreted in terms of degree of bond-formation at the transition state, which was found to have progressed relatively further. The rates for o-methylaniline deviated from the Bronsted plot established by meta and para substituted anilines because of a steric effect of ortho position in aniline. Activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ have also been determined. The enthalpy of activation showed a regular variation in that electron donating substituents in the p-substituted aniline decrease ${\Delta}H^{\neq}$ and increase the negative value of ${\Delta}S^{\neq}$.

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CoMFA Analysis on Inhibitory Effect of $3{\beta}$-Hydroxy-12-oleanen-28-oic Acid Analogues on PTP-1B Activity and Prediction of Active Compounds ($3{\beta}$-Hydroxy-12-oleanen-28-oic Acid 유도체들의 PTP-1B 저해활성에 대한 CoMFA 분석과 활성 분자들의 예측)

  • Kim, Sang-Jin;Kim, Se-Gon;Sung, Nack-Do
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.34 no.2
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    • pp.109-115
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    • 2008
  • The comparative molecular field analyses(CoMFA) models between the substituents with changing groups($R_1{\sim}R_4$) of $3{\beta}$-hydroxy-12-oleanen-28-oic acid derivatives as substrate molecule and their inhibitory activities($pI_{50}$) against protein tyrosine phosphatase(PTP)-1B were derived and discussed quantitatively. The optimized CoMFA F1 model have best predictability and fitness($r^2_{cv.}=0.654$ and $r^2_{ncv.}=0.995$). The order of contribution ratio (%) with CoMFA fields on the inhibitory activities was a steric field(53.0%), electrostatic field(36.2%) and hydrophobic field(10.8%). From the analytical results of CoMFA contour maps, the inhibitory activities were dependent on the R4 group in substrate molecules. Particularly, the new active compounds(P1 & P2) with the inhibitory activity against melanin synthesis were expected.

Effects of PVA and CMC addition on Rheological Characteristics and Curtain Stability of GCC Based Curtain Coating Colors (PVA와 CMC 첨가가 커튼 코팅용 GCC 도공액의 유변 특성 및 커튼 안정성에 미치는 영향)

  • Choi, Eun-Heui;Kim, Chae-Hoon;Lee, Hak-Lae
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.42 no.5
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    • pp.74-82
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    • 2010
  • Curtain stability without curtain contraction is critical for a successful operation in curtain coating, and this can be influenced by the change in particle dynamics and rheological properties of coating colors. In this study, polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC) were added to control the rheology of GCC based curtain coating colors. Surface tension was increased slightly with increasing content of cobinder. Shear-thinning of viscosity was more pronounced for the CMC containing GCC coating colors. Complex modulus decreased when small amount of PVA was used as a cobinder, but it increased in other coating colors. Extensional viscosity was increased with increasing of the cobinder content, but CMC was more effective. Results indicate that pigment interaction with PVA is different from that with CMC. Dispersibility of coating colors was improved due to steric stabilization when small amounts of PVA was used, but flocculation occurred by bridging when the amount of PVA was increased. Dispersibility of coating colors was improved when small amount of CMC was added, while flocculation was observed by depletion effect when the concentration of CMC was increased in coating colors. Addition of cobinders at proper levels gave positive effects both in rheological properties and curtain stability. On the other hand, excessive amount of cobinders caused particle flocculation and this resulted in rheological and curtain stablity problems.

Synthesis of Well-Defined Block Copolymer Dispersants with (2-Dimethylamino)ethyl Methacrylate and Oligo(ethylene oxide)methyl Ether Methacrylate via ATRP for Dispersing Copper Phthalocyanine Pigment (Copper Phthalocyanine Pigment의 분산을 위한 (2-Dimethylamino)ethyl Methacrylate와 Oligo(ethylene oxide)methyl Ether Methacrylate를 포함하는 잘 규정된 블록 공중합체형 분산제의 원자 이동 라디칼 중합을 이용한 합성)

  • Kim, Eun-Hee;Kim, Bong-Soo;Jung, Ki-Suk;Kim, Jin-Goo;Paik, Hyun-Jong
    • Polymer(Korea)
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    • v.36 no.1
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    • pp.104-110
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    • 2012
  • The dispersion of pigment particles is important because it is capable of increasing the color strength, contrast, and transmittance of color-LCD products. Pigment dispersion properties are very important factors for the quality of LCD color filters. The chemical structure of polymeric dispersants for pigment is important to improve dispersion stability and prevent aggregation or flocculation of pigment in organic or aqueous systems. Polymeric dispersants should contain both anchoring group that interacts with pigment surface and stabilizing group that provides steric stabilization. Moreover, the molecular weight and composition of block copolymer have the an effect on pigment dispersion. In this study, adequate dispersants, block copolymers containing (2-dimethylamino)ethyl methacrylate as anchoring group and oligo(ethylene oxide)methyl ether methacrylate as a stabilizing group were designed and synthesized by atom transfer radical polymerization in order to prepare well-defined structure, molecular weight and composition.

A New Functional Model of Catechol Dioxygenases: Properties and Reactivity of [Fe(BLPA)DBC]$BPh_4$

  • Lim, Ji H.;Lee, Ho J.;이강봉;Jang, Ho G.
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1166-1172
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    • 1997
  • [FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

The Effects of Hexamethylenetetramine Concentration on the Structural and Electrochemical Performances of Ni(OH)2 Powder for Pseudocapacitor Applications (헥사메틸렌테트라민 농도에 따른 수산화니켈 입자의 특성 분석 및 의사커패시터 응용)

  • Kim, Dong Yeon;Jeong, Young-Min;Baek, Seong-Ho;Son, Injoon
    • Journal of Powder Materials
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    • v.26 no.3
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    • pp.231-236
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    • 2019
  • Ni hydroxides ($Ni(OH)_2$) are synthesized on Ni foam by varying the hexamethylenetetramine (HMT) concentration using an electrodeposition process for pseudocapacitor (PC) applications. In addition, the effects of HMT concentration on the $Ni(OH)_2$ structure and the electrochemical properties of the PCs are investigated. HMT is the source of amine-based $OH^-$ in the solution; thus, the growth rate and morphological structure of $Ni(OH)_2$ are influenced by HMT concentration. When $Ni(OH)_2$ is electrodeposited at a constant voltage mode of -0.85 V vs. Ag/AgCl, the cathodic current and the number of nucleations are significantly reduced with increasing concentration of HMT from 0 to 10 mM. Therefore, $Ni(OH)_2$ is sparsely formed on the Ni foam with increasing HMT concentration, showing a layered double-hydroxide structure. However, loosely packed $Ni(OH)_2$ grains that are spread on Ni foam maintain a much greater surface area for reaction and result in the effective utilization of the electrode material due to the steric hindrance effect. It is suggested that the $Ni(OH)_2$ electrodes with HMT concentration of 7.5 mM have the maximum specific capacitance (1023 F/g), which is attributed to the facile electrolyte penetration and fast proton exchange via optimized surface areas.

Engineered nanoparticles in wastewater systems: Effect of organic size on the fate of nanoparticles

  • Choi, Soohoon;Chen, Ching-Lung;Johnston, Murray V.;Wang, Gen Suh;Huang, Chin-Pao
    • Membrane and Water Treatment
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    • v.13 no.1
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    • pp.29-37
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    • 2022
  • To verify the fate and transport of engineered nanoparticles (ENP), it is essential to understand its interactions with organic matter. Previous research has shown that dissolved organic matter (DOM) can increase particle stability through steric repulsion. However, the majority of the research has been focused on model organic matter such as humic or fulvic acids, lacking the understanding of organic matter found in field conditions. In the current study, organic matter was sampled from wastewater treatment plants to verify the stability of engineered nanoparticles (ENP) under field conditions. To understand how different types of organic matter may affect the fate of ENP, wastewater was sampled and separated based on their size; as small organic particular matter (SOPM) and large organic particular matter (LOPM), and dissolved organic matter (DOM). Each size fraction of organic matter was tested to verify their effects on nano-zinc oxide (nZnO) and nano-titanium oxide (nTiO2) stability. For DOM, critical coagulation concentration (CCC) experiments were conducted, while sorption experiments were conducted for organic particulates. Results showed that under field conditions, the surface charge of the particles did not influence the stability. On the contrary, surface charge of the particles influenced the amount of sorption onto particulate forms of organic matter. Results of the current research show how the size of organic matter influences the fate and transport of different ENPs under field conditions.

Chemical Reactions in Surfactant Solutions (II). Nucleophilic and Micellar Catalyses of Sodium 2-Alkylbenzimidazole-5-sulfonates on Hydrolyses of Carboxylic Esters in Aqueous and CTABr Solutions (계면활성제 용액속에서의 화학반응 (제 2 보). 카르복시산 에스테르의 가수 분해 반응에 미치는 2-알킬벤즈이미다졸-5-술포네이트의 친핵적 및 미셀효과)

  • Young Seuk Hong;Jeung Bae Kim;Hee Hyun Park;Dae Ryong Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.97-105
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    • 1989
  • This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

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