• Title/Summary/Keyword: nano-stabilization

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Kinetic Study on Aminolysis of Y-Substituted-Phenyl X-Substituted-Benzoates: Effects of Substituents X and Y on Reactivity and Reaction Mechanism

  • Jeon, Seong Hoon;Kim, Hyun Soo;Han, Young Joon;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.471-476
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    • 2014
  • A kinetic study on aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (2a-k) in 80 mol % $H_2O/_20mol%$ DMSO at $25.0^{\circ}C$ is reported. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (2g) with a series of cyclic secondary amines curves downward (e.g., ${\beta}_1=0.25$, ${\beta}_2=0.85$ and $pK_a^o=10.3$), which is typical of reactions reported to proceed through a stepwise mechanism with a change in ratedetermining step (RDS). The Hammett plot for the reactions of 2a-k with piperidine consists of two intersecting straight lines, while the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X=1.15$ and r = 0.59. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in RDS but is caused by stabilization of substrates through resonance interactions between the electron-donating substituent and the C=O bond. Substrates possessing a substituent at the 2-position of the leaving aryloxide deviate negatively from the curved Br${\emptyset}$nsted-type plot for the reactions of Y-substituted-phenyl benzoates (3a-i), implying that the steric hindrance exerted by the substituent at the 2-position is an important factor which governs the reactivity of Y-substituted-phenyl benzoates.

Decomposition of Paraoxon and Parathion by Amines, HOO- and OH- Ions: Reaction Mechanism and Origin of the α-Effect

  • Bae, Ae-Ri;Lee, Jieun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.201-206
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    • 2013
  • The second-order rate constants have been measured spectrophotometrically for the reactions of paraoxon 1 and parathion 2 with a series of alicyclic secondary amines, $OH^-$ and $HOO^-$ ions in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. A linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.40 was obtained for the reactions of 1 with amines and $OH^-$. The reaction has been concluded to proceed through a concerted mechanism. $HOO^-$ deviates positively from the linear Br${\o}$nsted-type plot, implying that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect ($k_{HOO^-}/k_{OH^-}$) was found to be ca. 55 for the reaction of 1 and 290 for that of parathion 2, indicating that $HOO^-$ is highly effective in decomposition of the toxic phosphorus compounds although it is over 4 $pK_a$ units less basic than $OH^-$. Among the theories suggested as origins of the ${\alpha}$-effect (e.g., TS stabilization through an intramolecular Hbonding interaction, solvent effect, and polarizability effect), polarizability effect appears to be the most important factor for the ${\alpha}$-effect in this study, since the polarizable $HOO^-$ exhibits a larger ${\alpha}$-effect for the reaction of the more polarizable substrate 2.

The α-Effect in Nucleophilic Substitution Reactions of Y-Substituted-Phenyl Diphenylphosphinates with HOO- and OH-

  • Hong, Hyo-Jeong;Bae, Ae Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2251-2255
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    • 2013
  • Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

Pectin Micro- and Nano-capsules of Retinyl Palmitate as Cosmeceutical Carriers for Stabilized Skin Transport

  • Ro, Jieun;Kim, Yeongseok;Kim, Hyeongmin;Park, Kyunghee;Lee, Kwon-Eun;Khadka, Prakash;Yun, Gyiae;Park, Juhyun;Chang, Suk Tai;Lee, Jonghwi;Jeong, Ji Hoon;Lee, Jaehwi
    • The Korean Journal of Physiology and Pharmacology
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    • v.19 no.1
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    • pp.59-64
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    • 2015
  • Retinyl palmitate (RP)-loaded pectinate micro- and nano-particles (PMP and PNP) were designed for stabilization of RP that is widely used as an anti-wrinkle agent in anti-aging cosmeceuticals. PMP/PNP were prepared with an ionotropic gelation method, and anti-oxidative activity of the particles was measured with a DPPH assay. The stability of RP in the particles along with pectin gel and ethanolic solution was then evaluated. In vitro release and skin permeation studies were performed using Franz diffusion cells. Distribution of RP in each skin tissue (stratum corneum, epidermis, and dermis) was also determined. PMP and PNP could be prepared with mean particle size diameters of $593{\sim}843{\mu}m$ (PMP) and 530 nm (i.e., $0.53{\mu}m$, PNP). Anti-oxidative activity of PNP was greater than PMP due largely to larger surface area available for PNP. The stability of RP in PMP and PNP was similar but much greater than RP in pectin bulk gels and ethanolic solution. PMP and PNP showed the abilities to constantly release RP and it could be permeated across the model artificial membrane and rat whole skin. RP was serially deposited throughout the skin layers. This study implies RP loaded PMP and PNP are expected to be advantageous for improved anti-wrinkle effects.

Controlled Synthesis of FeSe2 Nanoflakes Toward Advanced Sodium Storage Behavior Integrated with Ether-Based Electrolyte

  • Chen, Yalan;Zhang, Jingtong;Liu, Haijun;Wang, Zhaojie
    • Nano
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    • v.13 no.12
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    • pp.1850141.1-1850141.11
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    • 2018
  • Sodium ion batteries based on the more sodium source reserve than that of lithium have been designed as promising alternatives to lithium ion batteries. However, several problems including unsatisfied specific capacity and serious cyclic stability must be solved before the reality. One of the effective approaches to solve the abovementioned problems is to search for suitable anode materials. In this work, we designed and prepared $FeSe_2$ nanoflakes via a simple hydrothermal method which can be adjusted in composition by Fe precursor. As a potential anode for sodium storage, the optimized $FeSe_2$ electrode was further evaluated in different electrolytes of $NaClO_4$ in propylene carbonate/fluoroethylene carbonate and $NaCF_3SO_3$ in diethylene glycol dimethyl ether. The capacity was about $470mAh\;g^{-1}$ and $535mAh\;g^{-1}$ at $0.5A\;g^{-1}$, respectively, in the voltage between 0.5 V and 2.9 V in the cycle of stabilization phase. Superior performance both in capacity and in stability was obtained in ether-based electrolyte, which affords the property without plugging the intermediates of transition metal dichalcogenides during charge/discharge processes.

Nanowire Patterning for Biomedical Applications

  • Yun, Young-Sik;Lee, Jun-Young;Yeo, Jong-Souk
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.382-382
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    • 2012
  • Nanostructures have a larger surface/volume ratio as well as unique mechanical, physical, chemical properties compared to existing bulk materials. Materials for biomedical implants require a good biocompatibility to provide a rapid recovery following surgical procedure and a stabilization of the region where the implants have been inserted. The biocompatibility is evaluated by the degree of the interaction between the implant materials and the cells around the implants. Recent researches on this topic focus on utilizing the characteristics of the nanostructures to improve the biocompatibility. Several studies suggest that the degree of the interaction is varied by the relative size of the nanostructures and cells, and the morphology of the surface of the implant [1, 2]. In this paper, we fabricate the nanowires on the Ti substrate for better biocompatible implants and other biomedical applications such as artificial internal organ, tissue engineered biomaterials, or implantable nano-medical devices. Nanowires are fabricated with two methods: first, nanowire arrays are patterned on the surface using e-beam lithography. Then, the nanowires are further defined with deep reactive ion etching (RIE). The other method is self-assembly based on vapor-liquid-solid (VLS) mechanism using Sn as metal-catalyst. Sn nanoparticle solutions are used in various concentrations to fabricate the nanowires with different pitches. Fabricated nanowries are characterized using scanning electron microscopy (SEM), x-ray diffraction (XRD), and high resolution transmission electron microscopy (TEM). Tthe biocompatibility of the nanowires will further be investigated.

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Cytotoxic Activity of Biosynthesized Gold Nanoparticles with an Extract of the Red Seaweed Corallina officinalis on the MCF-7 Human Breast Cancer Cell Line

  • El-Kassas, Hala Yassin;El-Sheekh, Mostafa M.
    • Asian Pacific Journal of Cancer Prevention
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    • v.15 no.10
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    • pp.4311-4317
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    • 2014
  • Background: Nano-biotechnology is recognized as offering revolutionary changes in the field of cancer therapy and biologically synthesized gold nanoparticles are known to have a wide range of medical applications. Materials and Methods: Gold nanoparticles (GNPs) were biosynthesized with an aqueous extract of the red alga Corallina officinalis, used as a reducing and stabilizing agent. GNPs were characterized using UV-Vis spectroscopy, transmission electron microscopy (TEM), energy dispersive analysis (EDX) and Fourier transform infra-red (FT-IR) spectroscopy and tested for cytotoxic activity against human breast cancer (MCF-7) cells cultured in Dulbecco's modified Eagle medium supplemented with 10% fetal bovine serum, considering their cytotoxicty and effects on cellular DNA. Results: The biosynthesized GNPs were $14.6{\pm}1nm$ in diameter. FT-IR analysis showed that the hydroxyl functional group from polyphenols and carbonyl group from proteins could assist in formation and stabilization. The GNPs showed potent cytotoxic activity against MCF-7 cells, causing necrosis at high concentrations while lower concentrations were without effect as indicated by DNA fragmentation assay. Conclusions: The antitumor activity of the biosynthesized GNPs from the red alga Corallina officinalis against human breast cancer cells may be due to the cytotoxic effects of the gold nanoparticles and the polyphenolcontent of the algal extract.

OnBoard Vision Based Object Tracking Control Stabilization Using PID Controller

  • Mariappan, Vinayagam;Lee, Minwoo;Cho, Juphil;Cha, Jaesang
    • International Journal of Advanced Culture Technology
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    • v.4 no.4
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    • pp.81-86
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    • 2016
  • In this paper, we propose a simple and effective vision-based tracking controller design for autonomous object tracking using multicopter. The multicopter based automatic tracking system usually unstable when the object moved so the tracking process can't define the object position location exactly that means when the object moves, the system can't track object suddenly along to the direction of objects movement. The system will always looking for the object from the first point or its home position. In this paper, PID control used to improve the stability of tracking system, so that the result object tracking became more stable than before, it can be seen from error of tracking. A computer vision and control strategy is applied to detect a diverse set of moving objects on Raspberry Pi based platform and Software defined PID controller design to control Yaw, Throttle, Pitch of the multicopter in real time. Finally based series of experiment results and concluded that the PID control make the tracking system become more stable in real time.

The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization

  • Cho, Hyo-Jin;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2371-2374
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    • 2014
  • A kinetic study is reported on SNAr reaction of 1-fluoro-2,4-dinitrobenzene with a series of primary amines including hydrazine in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{obsd}$ vs. [amine] are linear and pass through the origin, indicating that general-base catalysis by a second amine molecule is absent. The Br${\o}$nsted-type plot exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.46 when hydrazine is excluded from the correlation. The reaction has been suggested to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step (RDS). Hydrazine is ca. 10 times more reactive than similarly basic glycylglycine (i.e., the ${\alpha}$-effect). A five-membered cyclic intermediate has been suggested for the reaction with hydrazine, in which intramolecular H-bonding interactions would facilitate expulsion of the leaving group. However, the enhanced leaving-group ability is not responsible for the ${\alpha}$-effect shown by hydrazine because expulsion of the leaving group occurs after RDS. Destabilization of the ground-state of hydrazine through the electronic repulsion between the nonbonding electron pairs is responsible for the ${\alpha}$-effect found in the current $S_NAr$ reaction.

Effect of Process Variables and exisisting Ions on Highly Active Nano-sized ITO Powders Prepared by Precipitation Method (고활성 ITO (Indium-Tin Oxide) 나노 분말을 침전법으로 합성시의 공정 변수 및 존재하는 이온의 영향)

  • Lee, In-Gyu;Noh, Bong-Hyun
    • Journal of Powder Materials
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    • v.15 no.6
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    • pp.450-457
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    • 2008
  • The objectives of this study were the development of a synthesis technique for highly active nanosized ITO powder and the understanding of the reaction mechanisms of the ITO precursors. The precipitation and agglomeration phenomena in ITO and $In_{2}O_{3}$ precursors are very sensitive to reaction temperature, pH, and coexisting ion species. Excessive $Cl^-$ ion and $Sn^{+4}$ ions had a negative effect an synthesizing highly active powders. However, with a relevant stabilizing treatment the shape and size of ITO and $In_{2}O_{3}$ precursors could be controlled and high density sintered products of ITO were obtained. By applying the reprecipitation process (or stabilization technique), highly active ITO and $In_{2}O_{3}$ powders were synthesized. Sintering these powders at $1500^{\circ}C$ for 5 hours produced 97% dense ITO bodies.