• Title/Summary/Keyword: Steric hindrance

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Quantitative Analysis of Grafted Methacrylate Groups by Michael Addition Reaction between Primary and Secondary Amino Groups on the Silica Nanoparticle Surface with 3-(Acryloyloxy)-2-Hydroxypropyl Methacrylate (실리카 나노 입자 표면에 결합된 1차 및 2차 아미노기와 3-(Acryloyloxy)-2-hydroxypropyl Methacrylate의 마이클 부가 반응에 의해 도입되는 메타크릴레이트기의 정량적 분석)

  • Lee, Sangmi;Ha, KiRyong
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.300-310
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    • 2015
  • In this study, we modified silica nanoparticles with N-[3-(trimethoxysilyl)propyl]ethylenediamine (TPED) silane coupling agent, which has one primary and one secondary amino groups in a molecule, to introduce amino groups on the silica surface. After modification of silica, we used 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce methacrylate groups by Michael addition reaction. We found about 30% of N-H groups on the TPED modified silica surface reacted with acrylate groups of AHM compared to about 85% of reaction between N-H groups of pure TPED with acrylate groups of pure AHM. This lower degree of Michael addition reaction for heterogeneous reaction between N-H groups on the solid TPED modified silica and liquid AHM compared to homogeneous reaction between pure liquid TPED and pure liquid AHM may be caused by lower mobility of grafted amino groups of TPED moiety and higher steric hindrance caused by solid silica particles.

Host-Guest Interactions of Cyclic and Acyclic Polyethers with Alkylammonium Ions (고리 및 비고리 폴리에테르와 알킬암모늄 이온과의 호스트-게스트 상호작용)

  • Jeong, Jong Hwa;Kim, Dae Yeon;Lee, Sim Seong
    • Journal of the Korean Chemical Society
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    • v.38 no.7
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    • pp.509-515
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    • 1994
  • The interactions of 11 kinds of primary and secondary alkylammonium ions with cyclic (12C4, 15C5, 18C6, DT18C6 and DA18C6) and acyclic$(Q_2O_5)$ polyethers were investigated by NMR titration and conductometry. All of the alkylammonium ions under investigation form the relatively stable 1 : 1 complexes with crown ethers and acyclic polyether by H-bond. The interactions of alkylammonium ions with analogeous hosts having different size were in the order of 18C6 > 15C5 > 12C4, and the strengthes of donor atoms toward the alkylammonium ions were in the order of N > O > S. 18C6 forms more favorable interactions with primary alkylammonium ions than secondary alkylammonium ions, otherwise DA18C6 shows the opposite behaviors. The stability constants for complexations of 18C6 with the alkylammonium ions were determined conductometrically in methanol at 25$^{\circ}C$. The major factors affecting the stability of complexes were the type of alkylammonium ions, the length of alkyl-chain and the steric hindrance due to the structure of alkyl groups on complexation.

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Quantitative Assay of Recombinant Hepatitis B Surface Antigen by Using Surface Plasmon Resonance Biosensor (Surface plasmon resonance 바이오센서를 이용한 재조합 B형 간염 표면항원의 정량분석)

  • Lee, E. K.;Ahn, S. J.;Yoo, C. H.;Ryu, K.;Jeon, J. Y.;Lee, H. I.;Choi, S. C.;Lee, Y. S.
    • KSBB Journal
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    • v.17 no.1
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    • pp.20-25
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    • 2002
  • We performed a basic experiment for rapid, on-line, real-time measurement of HBsAg by using a surface plasmon resonance biosensor to quantify the recognition and interaction of biomolecules. We immobilized the anti-HBsAg polyclonal antibody to the dextran layer on a CM5 chip surface which was pre-activated by N-hydroxysuccinimide for amine coupling. The binding of the HBsAg to the immobilized antibody was measured by the mass increase detected by the change in the SPR signal. The binding characteristics between HBsAg and its antibody followed typical monolayer adsorption isotherm. When the entire immobilized antibody was interacted, there was no additional, non-specific binding observed, which suggested the biointeraction was very specific as expected and independent of the ligand density. No significant steric hindrance was observed at 17.6 nm/$mm^2$ immobilization density. The relationship between the HBsAg concentration in the sample solution and the antigen bound to the chip surface was linear up to ca. $40\mu\textrm{g}$/mL, which is much wider than that of the ELISA method. It appeared the antigen-antibody binding was increased as the immobilized ligand density increased, but verification is warranted. This study showed the potential of this biosensor-based method as a rapid, simple, multi-sample, on-line assay. Once properly validated, it can serve as a more powerful method for HBsAg quantification replacing the current ELISA method.

Computational and experimental characterization of estrogenic activities of 20(S, R)-protopanaxadiol and 20(S, R)-protopanaxatriol

  • Zhang, Tiehua;Zhong, Shuning;Hou, Ligang;Wang, Yongjun;Xing, XiaoJia;Guan, Tianzhu;Zhang, Jie;Li, Tiezhu
    • Journal of Ginseng Research
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    • v.44 no.5
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    • pp.690-696
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    • 2020
  • Background: As the main metabolites of ginsenosides, 20(S, R)-protopanaxadiol [PPD(S, R)] and 20(S, R)-protopanaxatriol [PPT(S, R)] are the structural basis response to a series of pharmacological effects of their parent components. Although the estrogenicity of several ginsenosides has been confirmed, however, the underlying mechanisms of their estrogenic effects are still largely unclear. In this work, PPD(S, R) and PPT(S, R) were assessed for their ability to bind and activate human estrogen receptor α (hERα) by a combination of in vitro and in silico analysis. Methods: The recombinant hERα ligand-binding domain (hERα-LBD) was expressed in E. coli strain. The direct binding interactions of ginsenosides with hERα-LBD and their ERα agonistic potency were investigated by fluorescence polarization and reporter gene assays, respectively. Then, molecular dynamics simulations were carried out to simulate the binding modes between ginsenosides and hERα-LBD to reveal the structural basis for their agonist activities toward receptor. Results: Fluorescence polarization assay revealed that PPD(S, R) and PPT(S, R) could bind to hERα-LBD with moderate affinities. In the dual luciferase reporter assay using transiently transfected MCF-7 cells, PPD(S, R) and PPT(S, R) acted as agonists of hERα. Molecular docking results showed that these ginsenosides adopted an agonist conformation in the flexible hydrophobic ligand-binding pocket. The stereostructure of C-20 hydroxyl group and the presence of C-6 hydroxyl group exerted significant influence on the hydrogen bond network and steric hindrance, respectively. Conclusion: This work may provide insight into the chemical and pharmacological screening of novel therapeutic agents from ginsenosides.

The Solid Phase Extraction of Phenol and Chlorophenols by the Chemically Modified Polymeric Adsorbents with Porphyrins

  • Jung, Min-Woo;Kim, Ki-Pal;Cho, Byung-Yun;Paeng, Insook R.;Lee, Dai-Woon;Park, Young-Hun;Paeng, Ki-Jung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.1
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    • pp.77-81
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    • 2006
  • The commercially available Amberlite XAD-2 and XAD-4 resins were modified with macrocyclic protoporphyrin IX (PPIX) or tetrakis(p-carboxyphenyl) porphyrin (TCPP) to enhance the adsorption capacity for phenol and chlorophenols. The chemically modified polymeric adsorbents (XAD-2+PPIX, XAD-2+TCPP, XAD-4+PPIX, and XAD-4+TCPP) were applied to the solid phase extraction as an adsorbent material for the preconcentration of phenol and chlorophenols in environmental waters. Generally, the synthesized adsorbents showed higher recoveries than underivatized adsorbents, XAD-2 and XAD-4, without matrix interferences. Especially, XAD-4+PPIX showed more than 90% recoveries for all compounds used in this study including hydrophilic phenol. The major factor for the increase of the adsorption capacity was the increase of $\pi$-$\pi$ interaction between adsorbents and samples due to the introduction of the porphyrin molecule. However, the breakthrough volumes and recovery values of the XADs+TCPP columns were slightly decreased for the bulky chlorophenols such as TCP and PCP. Using molecular mechanics methods, the structures of TCPP and PPIX were compared with that of porphine, the parent molecule of porphyrin. Four bulky p-carboxyphenyl groups of TCPP were torsional each other, thus the molecular plane of TCPP were not on the same level. In conclusion, the decrease of breakthrough volumes and recovery values of XADs+TCPP columns for bulky phenols can be explained by the steric hindrance of the $\pi$-$\pi$ interaction between porphyrin plane and the phenols.

Non-volatile Molecular Memory using Nano-interfaced Organic Molecules in the Organic Field Effect Transistor

  • Lee, Hyo-Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.31-32
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    • 2010
  • In our previous reports [1-3], electron transport for the switching and memory devices using alkyl thiol-tethered Ru-terpyridine complex compounds with metal-insulator-metal crossbar structure has been presented. On the other hand, among organic memory devices, a memory based on the OFET is attractive because of its nondestructive readout and single transistor applications. Several attempts at nonvolatile organic memories involve electrets, which are chargeable dielectrics. However, these devices still do not sufficiently satisfy the criteria demanded in order to compete with other types of memory devices, and the electrets are generally limited to polymer materials. Until now, there is no report on nonvolatile organic electrets using nano-interfaced organic monomer layer as a dielectric material even though the use of organic monomer materials become important for the development of molecularly interfaced memory and logic elements. Furthermore, to increase a retention time for the nonvolatile organic memory device as well as to understand an intrinsic memory property, a molecular design of the organic materials is also getting important issue. In this presentation, we report on the OFET memory device built on a silicon wafer and based on films of pentacene and a SiO2 gate insulator that are separated by organic molecules which act as a gate dielectric. We proposed push-pull organic molecules (PPOM) containing triarylamine asan electron donating group (EDG), thiophene as a spacer, and malononitrile as an electron withdrawing group (EWG). The PPOM were designed to control charge transport by differences of the dihedral angles induced by a steric hindrance effect of side chainswithin the molecules. Therefore, we expect that these PPOM with potential energy barrier can save the charges which are transported to the nano-interface between the semiconductor and organic molecules used as the dielectrics. Finally, we also expect that the charges can be contributed to the memory capacity of the memory OFET device.[4]

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Molecular Signature That Determines the Acute Tolerance of G Protein-Coupled Receptors

  • Min, Chengchun;Zhang, Xiaohan;Zheng, Mei;Sun, Ningning;Acharya, Srijan;Zhang, Xiaowei;Kim, Kyeong-Man
    • Biomolecules & Therapeutics
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    • v.25 no.3
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    • pp.239-248
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    • 2017
  • Desensitization and acute tolerance are terms used to describe the attenuation of receptor responsiveness by prolonged or intermittent exposure to an agonist. Unlike desensitization of G protein-coupled receptors (GPCRs), which is commonly explained by steric hindrance caused by the ${\beta}$-arrestins that are translocated to the activated receptors, molecular mechanisms involved in the acute tolerance of GPCRs remain unclear. Our studies with several GPCRs and related mutants showed that the acute tolerance of GPCRs could occur independently of agonist-induced ${\beta}$-arrestin translocation. A series of co-immunoprecipitation experiments revealed a correlation between receptor tolerance and interactions among receptors, ${\beta}$-arrestin2, and $G{\beta}{\gamma}$. $G{\beta}{\gamma}$ displayed a stable interaction with receptors and ${\beta}$-arrestin2 in cells expressing GPCRs that were prone to undergo tolerance compared to the GPCRs that were resistant to acute tolerance. Strengthening the interaction between $G{\beta}{\gamma}$ and ${\beta}$-arrestin rendered the GPCRs to acquire the tendency of acute tolerance. Overall, stable interaction between the receptor and $G{\beta}{\gamma}$ complex is required for the formation of a complex with ${\beta}$-arrestin, and determines the potential of a particular GPCR to undergo acute tolerance. Rather than turning off the signal, ${\beta}$-arrestins seem to contribute on continuous signaling when they are in the context of complex with receptor and $G{\beta}{\gamma}$.

Study of Corrosion of Brass Coated Steel Cords in the Acetonitrile Solution of Sulfenamide Derivatives by Tafel Plot and AC Impedance Measurements

  • Young Chun Ko;Byung Ho Park;Hae Jin Kim;Q Won Choi;Jongbaik Ree;Keun Ho Chung
    • Bulletin of the Korean Chemical Society
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    • v.15 no.2
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    • pp.122-126
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    • 1994
  • Corrosion of brass coated steel cords in the acetonitrile solution of sulfenamide derivatives, N-Cyclohexylbenzothiazole-2-sulfenamide (CBTS), N,N'-Dicyclohexylbenzothiazole-2-sulfenamide (DCBS), N-tert-Butylbenzothiazole-2-sulfenamide (TBBS), N-tert-Amylbenzothiazole-2-sulfenamide (TABS), and N-Oxydiethylbenzothiazole-2-sulfenamide (OBTS) was investigated by potentiostatic anodic and cathodic polarization (Tafel plot), DC polarization resistance, and AC impedance measurements. The corrosion current densities and rates are 1.236 ${\mu}A /cm^2$ and 0.655 MPY for CBTS; 1.881 ${\mu}A/cm^2$ and 0.988 MPY for DCBS; 2.367 ${\mu}A/cm^2$ and 1.257 MPY for TBBS; 3.398 ${\mu}A /cm^2$ and 1.809 MPY for TABS, respectively. OBTS among derivatives under study shows the lowest corrosion density (0.546 ${\mu}A /cm^2$) and the slowest corrosion rate (0.288 MPY). Also, the charge transfer resistances and the double layer capacitances are 275.21 $k{\Omega}{\cdot}cm^2$ and 7.0 ${\mu}F{cdot}cm^{-2}$ for CBTS; 14.24 ${\mu}F{\cdot}cm^2$ and 26 ${\mu}F{\cdot}cm^{-2}$ for DCBS; 54.15 $k{\Omega}{\cdot}cm^2$ and 26 ${\mu}F{\cdot}cm^{-2}$ for TBBS; 0.96$k{\Omega}{\cdot}cm^2$ and 83 ${\mu}F{\cdot}cm^{-2}$ for TABS, respectively. The weaker the electron donating inductive effect of derivatives is and the smaller the effect of steric hindrance is, the more the corrosion of brass coated steel cords in the acetonitrile solution of sulfenamide derivatives is prevented. The above results agree with that observed in the field of tire industry.

Platinum-Catalyzed and Ion-Selective Polystyrene Fibrous Membrane by Electrospinning and In-Situ Metallization Techniques

  • Hong, Seung-Hee;Lee, Sun-Ae;Nam, Jae-Do;Lee, Young-Kwan;Kim, Tae-Sung;Won, Sung-Ho
    • Macromolecular Research
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    • v.16 no.3
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    • pp.204-211
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    • 2008
  • A platinum-catalyzed polyelectrolyte porous membrane was prepared by solid-state compression of electrospun polystyrene (PS) fibers and in-situ metallization of counter-balanced ionic metal sources on the polymer surface. Using this ion-exchange metal-polymer composite system, fiber entangled pores were formed in the interstitial space of the fibers, which were surrounded by sulfonic acid sites ($SO_3^-$) to give a cation-selective polyelectrolyte porous bed with an ion exchange capacity ($I_{EC}$) of 3.0 meq/g and an ionic conductivity of 0.09 S/cm. The Pt loading was estimated to be 16.32 wt% from the $SO_3^-$ ions on the surface of the sulfonated PS fibers, which interact with the cationic platinum complex, $Pt(NH_3)_4^{2+}$, at a ratio of 3:1 based on steric hindrance and the arrangement of interacting ions. This is in good agreement with the Pt loading of 15.82 wt% measured by inductively coupled plasma-optical emission spectroscopy (ICP-OES). The Pt-loaded sulfonated PS media showed an ionic conductivity of 0.32 S/cm. The in-situ metallized platinum provided a nano-sized and strongly-bound catalyst in robust porous media, which highlights its potential use in various electrochemical and catalytic systems.

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.