• Title/Summary/Keyword: cyclic group

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Metal-Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Thionobenzoate: Effects of Modification of Electrophilic Center from C=O to C=S

  • Um, Ik-Hwan;Song, Yoon-Ju;Kim, Min-Young;Lee, Jae-In
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1525-1529
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    • 2013
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

Synthesis and Effect on t-Butyl PBD of the Blue Light Emitting Poly(phenyl-9,9-dioctyl-9',9'-dihexanenitrile) fluorene

  • Kim Byong-Su;Kim Chung-Gi;Oh Jea-Jin;Kim Min-Sook;Kim Gi-Won;Park Dong-Kyu;Woo Hyung-Suk
    • Macromolecular Research
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    • v.14 no.3
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    • pp.343-347
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    • 2006
  • A novel, blue light-emitting polymer, poly(phenyl-9,9-dioctyl-9',9'dihexanenitrile)fluorene (PPFC6N), containing an alkyl and cyano group in the side chain, was synthesized by Suzuki polymerization and characterized. The polymer structure was confirmed by $^1H-NMR$. The number average molecular weight and the weight average molecular weight of the obtained polymer were 9,725 and 9,943 respectively. The resulting polymer was thermally stable with a glass transition temperature ($T_g$) of $93^{\circ}C$, and was easily soluble in common organic solvents such as THF, toluene, chlorobenzene and chloroform. The HOMO and LUMO energy levels of the polymer were revealed as 5.8 and 2.88 eV by cyclic voltammetry study, respectively. The ITO/PEDOT:PSS (40 nm)/PPFC6N (80 m)/LiF (1 nm)/Al (150 nm) device fabricated from the polymer emitted a PL spectrum at 450 nm and showed a real blue emission for pure PPFC6N in the EL spectrum. When t-butyl PBD was introduced as a hole blocking layer, the device performance was largely improved and the EL spectrum was slightly shifted toward deep blue. The device with PPFC6N containing t-butyl PBD layer showed the maximum luminance of 3,200 $cd/m^2$ at 9.5 V with a turnon voltage of 7 V.

Photophysical Properties of a Conjugated Poly(1-dodecyl-2,5-pyrrylene vinylene)

  • Park, Chang-Shik;Kim, In-Tae;Lee, Sang-Woo;Lee, Ha-Hyeong;Lee, Young-Nam;Jeon, Ki-Seok;Lee, Ki-Hwan;Sung, Nack-Do;Kil, Mun-Jae
    • Macromolecular Research
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    • v.12 no.3
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    • pp.322-324
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    • 2004
  • Poly(1-dodecyl-2,5-pyrrylene vinylene) (PDPV) has an extended 1t-conjugated structure and exhibits characteristic spectroscopic features. The PDPV we prepared has an absorption maximum at 510nm and its long absorption tail at ca. 750nm in methylene chloride is due to the long 1t-conjugated system connected to vinyl group. The large red-shift of emission was 625nm upon excitation at 480nm, which suggests the existence of a low emissive state. The emission of PDPV in less-polar solvents decreased markedly relative to that in the more-polar solvents; this observation was ascribed possibly to quenching by a strong vibrational mode of the dodecyl groups of PDPV in less-polar solvents. Furthermore, the emission from the high-energy side had a single decay component (0.1㎱, 49.96%), while that from the low-energy side had two components (0.6㎱, 27.1 %; 2.7㎱, 22.87%). We characterized the redox properties of PDPV by cyclic voltammetry. Every redox peak showed irreversible behavior; the oxidation peaks appeared at 1.7,0.8, and 0.6V and the reduction peak at -0.5V.

Seismic Performance of Precast Concrete Beam-Column Connections Using Ductile Rod (연성 강봉을 사용한 프리캐스트 콘크리트 보-기둥 접합부의 내진성능)

  • Lee, Sang-Jin;Hong, Sung-Gul;Lim, Woo-Young
    • Journal of the Korea Concrete Institute
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    • v.26 no.6
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    • pp.695-705
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    • 2014
  • Precast concrete (PC) beam-column connections using ductile rods are proposed for earthquake zone. An existing beam-column connection, two PC specimens designed by considering failure modes and a conventional RC specimen were tested under cyclic loading to evaluate the seismic performance. The specimens were designed to satisfy the requirements of current design code. The variables are the yield strength of longitudinal reinforcing bars of PC beams. The test results showed that the proposed system applying smaller yield strength of the longitudinal reinforcing bars at the PC beams than the ductile rods was satisfied with seismic criteria. The deformation capacity and energy dissipation capacity of the proposed PC beam-column connections were greater than those of the existing DDC system.

Characteristics of Ring-Opening Isomerization Polymerization of [4.3.0] Cyclic Pseudoureas ([4.3.0] 환상 유사 우레아의 이성화 개환중합과 특성평가)

  • Lee, Chan-Woo;Chung, Jin-Do
    • Polymer(Korea)
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    • v.35 no.4
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    • pp.308-313
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    • 2011
  • The ring-opening isomerization polymerization behavior of 2,5,6,7-tetrahydro-3H-imidazo[2,1-b] [1,3] oxazine(TII) has been studied under various conditions. The present study aimed at improving the low polymerizability of the above monomer (six-membered ring) up to a level comparable to that of 2,5,6-tetrahydroimidazo[2,1-b] [l,3] oxazole(TIO) (five-membered ring). The optimum result could be observed when methyl trifluoromethanesulfonate(MeOTf) and nitrobenzene were used as an initiator and a solvent in the polymerization at $60^{\circ}C$ for 24 h. Polymers were confirmed by$^1H$ NMR과$^{13}C$ NMR, and m measurements. The molecular weight obtained by gel permeation chromatography (GPC) corresponded to the molecular weight theoretically calculated from the feed ratio. The melting temperature ($T_m$) of TII was conspicuously different from that of TIO, because of the difference in the alkyl group.

Cathodic Properties of $LiCoO_2$ Synthesized by a Sol-Gel Method for Lithium Ion Battery

  • 조봉준;정의덕;심윤보
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.39-44
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    • 1998
  • $LiCoO_2$ powder was synthesized in an aqueous solution by a sol-gel method and used as a cathode active material for a lithium ion rechargeable battery. The layered $LiCoO_2$ powders were prepared by igniting in air for 12 hrs at 600 ℃ $(600-LiCoO_2)$ and 850 ℃ $(850-LiCoO_2)$. The structure of the $LiCoO_2$ powder was assigned to the space group R bar 3 m (lattice parameters a=2.814 Å and c=14.04Å). The SEM pictures of $600-LiCoO_2$ revealed homogeneous and fine particles of about 1 μm in diameter. Cyclic voltammograms (CVs) of $600-LiCoO_2$ electrode displayed a set of redox peaks at 3.80/4.05 V due to the intercalation/deintercalation of the lithium ions into/out of the $LiCoO_2$ structure. CVs for the $850-LiCoO_2$ electrode had a major set of redox peaks at 3.88/4.13 V, and two small set of redox peaks at 4.18/4.42 V and 4.05/4.25 V due to phase transitions. The initial charge-discharge capacity was 156-132 mAh/g for the $600-LiCoO_2$ electrode and 158-131 mAh/g for the $850-LiCoO_2$ electrode at the current density of 0.2 mA/cm2. The cycleability of the cell consisting of the $600-LiCoO_2$ electrode was better than that of the $850-LiCoO_2$. The diffusion coefficient of the $Li^+$ ion in the $600-LiCoO_2$ electrode was calculated as $4.6{\times}10^{-8}\; cm^2/sec$.

Reduction of Inflammation and Enhancement of Motility after Pancreatic Islet Derived Stem Cell Transplantation Following Spinal Cord Injury

  • Karaoz, Erdal;Tepekoy, Filiz;Yilmaz, Irem;Subasi, Cansu;Kabatas, Serdar
    • Journal of Korean Neurosurgical Society
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    • v.62 no.2
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    • pp.153-165
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    • 2019
  • Objective : Spinal cord injury (SCI) is a very serious health problem, usually caused by a trauma and accompanied by elevated levels of inflammation indicators. Stem cell-based therapy is promising some valuable strategies for its functional recovery. Nestin-positive progenitor and/or stem cells (SC) isolated from pancreatic islets (PI) show mesenchymal stem cell (MSC) characteristics. For this reason, we aimed to analyze the effects of rat pancreatic islet derived stem cell (rPI-SC) delivery on functional recovery, as well as the levels of inflammation factors following SCI. Methods : rPI-SCs were isolated, cultured and their MSC characteristics were determined through flow cytometry and immunofluorescence analysis. The experimental rat population was divided into three groups : 1) laminectomy & trauma, 2) laminectomy & trauma & phosphate-buffered saline (PBS), and 3) laminectomy+trauma+SCs. Green fluorescent protein (GFP) labelled rPI-SCs were transplanted into the injured rat spinal cord. Their motilities were evaluated with Basso, Beattie and Bresnahan (BBB) Score. After 4-weeks, spinal cord sections were analyzed for GFP labeled SCs and stained for vimentin, $S100{\beta}$, brain derived neurotrophic factor (BDNF), 2',3'-cyclic-nucleotide 3'-phosphodiesterase (CNPase), vascular endothelial growth factor (VEGF) and proinflammatory (interleukin [IL]-6, transforming growth factor $[TGF]-{\beta}$, macrophage inflammatory protein [MIP]-2, myeloperoxidase [MPO]) and anti-inflammatory (IL-1 receptor antagonis) factors. Results : rPI-SCs were revealed to display MSC characteristics and express neural and glial cell markers including BDNF, glial fibrillary acidic protein (GFAP), fibronectin, microtubule associated protein-2a,b (MAP2a,b), ${\beta}3$-tubulin and nestin as well as anti-inflammatory prostaglandin E2 receptor, EP3. The BBB scores showed significant motor recovery in group 3. GFP-labelled cells were localized on the injury site. In addition, decreased proinflammatory factor levels and increased intensity of anti-inflammatory factors were determined. Conclusion : Transplantation of PI-SCs might be an effective strategy to improve functional recovery following spinal cord trauma.

Seismic Performance Evaluation of Dry Precast Concrete Beam-Column Connections With Intermediate Moment Frame Details (중간모멘트골조 상세를 갖는 건식 프리캐스트 콘크리트 보-기둥 접합부의 내진성능평가)

  • Kim, Seon Hoon;Cho, Jong;Oh, Hyo Keun;Choi, Seok Dong;Yeo, Un Yong;Lee, Deuck Hang
    • Journal of the Earthquake Engineering Society of Korea
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    • v.27 no.3
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    • pp.129-137
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    • 2023
  • This study presents a dry precast concrete (PC) beam-column connection, and its target seismic performance level is set to be emulative to the reinforced concrete (RC) intermediate moment resisting frame system specified in ACI 318 and ASCE 7. The key features include self-sustaining ability during construction with the dry mechanical splicing method, enabling emulative connection performances and better constructability. Test specimens with code-compliant seismic details were fabricated and tested under reversed cyclic loading, which included a PC beam-column connection specimen with dry connections and an RC control specimen. The test results showed that all the specimens failed in a similar failure mode due to plastic deformations in beam members, while the hysteretic response curve of the PC specimen showed comparable and emulative performances compared to the RC specimen. Seismic performance evaluation was quantitatively addressed, and on this basis, it confirmed that the presented system can fully satisfy all the required performance for the intermediate RC moment resisting frame.

Calcium annealing approach to control of surface groups and formation of oxide in Ti3C2Tx MXene

  • Jung-Min Oh;Su Bin Choi;Taeheon Kim;Jikwang Chae;Hyeonsu Lim;Jae-Won Lim;In-Seok Seo;Jong-Woong Kim
    • Advances in nano research
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    • v.15 no.1
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    • pp.1-13
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    • 2023
  • Ti3C2Tx MXene, a 2D material, is known to exhibit unique characteristics that are strongly dependent on surface termination groups. Here, we developed a novel annealing approach with Ca as a reducing agent to simultaneously remove F and O groups from the surface of multilayered MXene powder. Unlike H2 annealing that removes F effectively but has difficulty in removing O, annealing with Ca effectively removed both O and F. X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy revealed that the proposed approach effectively removed F and O from the MXene powder. The results of O/N analyses showed that the O concentration decreased by 57.5% (from 2.66 to 1.13 wt%). In addition, XPS fitting showed that the volume fraction of metal oxides (TiO2 and Al2O3) decreased, while surface termination groups (-O and -OH) were enhanced, which could increase the hydrophilic and adsorption properties of the MXene. These findings suggest that when F and O are removed from the MXene powder, the interlayer spacing of its lattice structure increases. The proposed treatment also resulted in an increase in the specific surface area (from 5.17 to 10.98 m2/g), with an increase in oxidation resistance temperature in air from ~436 to ~667 ℃. The benefits of this novel technology were verified by demonstrating the significantly improved cyclic charge-discharge characteristics of a lithium-ion battery with a Ca-treated MXene electrode.

Prediction of tensile strength degradation of corroded steel based on in-situ pitting evolution

  • Yun Zhao;Qi Guo;Zizhong Zhao;Xian Wu;Ying Xing
    • Steel and Composite Structures
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    • v.46 no.3
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    • pp.385-401
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    • 2023
  • Steel is becoming increasingly popular due to its high strength, excellent ductility, great assembly performance, and recyclability. In reality, steel structures serving for a long time in atmospheric, industrial, and marine environments inevitably suffer from corrosion, which significantly decreases the durability and the service life with the exposure time. For the mechanical properties of corroded steel, experimental studies are mainly conducted. The existing numerical analyses only evaluate the mechanical properties based on corroded morphology at the isolated time-in-point, ignoring that this morphology varies continuously with corrosion time. To solve this problem, the relationships between pit depth expectation, standard deviation, and corrosion time are initially constructed based on a large amount of wet-dry cyclic accelerated test data. Successively, based on that, an in-situ pitting evolution method for evaluating the residual tensile strength of corroded steel is proposed. To verify the method, 20 repeated simulations of mass loss rates and mechanical properties are adopted against the test results. Then, numerical analyses are conducted on 135 models of corrosion pits with different aspect ratios and uneven corrosion degree on two corroded surfaces. Results show that the power function with exponents of 1.483 and 1.091 can well describe the increase in pit depth expectation and standard deviation with corrosion time, respectively. The effect of the commonly used pit aspect ratios of 0.10-0.25 on yield strength and ultimate strength is negligible. Besides, pit number ratio α equating to 0.6 is the critical value for the strength degradation. When α is less than 0.6, the pit number increases with α, accelerating the degradation of strength. Otherwise, the strength degradation is weakened. In addition, a power function model is adopted to characterize the degradation of yield strength and ultimate strength with corrosion time, which is revised by initial steel plate thickness.