• Title/Summary/Keyword: O-O bond formation

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Characterization on the Ozone Oxidation of Raw Natural Rubber Thin Film using Image and FT-IR Analysis

  • Kim, Ik-Sik;Lee, DooYoul;Sohn, Kyung-Suk;Lee, Jung-Hun;Bae, JoongWoo
    • Elastomers and Composites
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    • v.54 no.2
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    • pp.110-117
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    • 2019
  • The characterization of the ozone oxidation for raw natural rubber (NR) was investigated under controlled conditions through image and fourier transform infrared (FT-IR) analysis. The ozone oxidation was performed on a transparent thin film of raw NR coated on a KBr window in a dark chamber at $40^{\circ}C$ under low humidity conditions to completely exclude thermal, moisture, or light oxidation. The ozone concentration was set at 40 parts per hundred million (pphm). Before or after exposure to ozone, the image of the thin film for raw NR was observed at a right or tilted angle. FT-IR absorption spectra were measured in the transmission mode according to ozone exposure time. The ozone oxidation of NR was determined by the changes in the absorption peaks at 1736, 1715, 1697, and $833cm^{-1}$, which were assigned to an aldehyde group (-CHO), a ketone group (-COR), an inter-hydrogen bond between carbonyl group (-C=O) from an aldehyde or a ketone and an amide group (-CONH-) of protein, and a cis-methine group ($is-CCH_3=CH-$, respectively. During ozone exposure period, the results indicated that the formation of the carbonyl group of aldehyde or ketone was directly related to the decrement of the double bond of cis-1,4-polyisoprene. Only carbonyl compounds such as aldehydes or ketones seemed to be formed through chain scission by ozone. Long thin cracks with one orientation at regular intervals, which resulted in consecutive chain scission, were observed by image analysis. Therefore, one possible two-step mechanism for the formation of aldehyde and ketone was suggested.

Kinetics and Mechanism for Aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3^-$, NO$_2$, NCS$^-$, H$_2$O} in Hg$^{2+}$ Aqueous Solution ($Hg^{2+}$ 수용액 내에서 cis-[Co(en)$_2$YCl]$^{r+}$ (Y = $NH_3$, NO$_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도와 반응메카니즘)

  • Byung-Kak Park;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.476-482
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    • 1988
  • Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

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The Availability of Automobile Catalytic Convert of Copper Based on the DFT Calculations of Cu-NO Complexes (Cu-NO 복합체에 대한 DFT 계산에 따른 Cu의 자동차 촉매변환기 적합성)

  • Ha, Kwanga;Lee, Min-Joo
    • Journal of the Korean Chemical Society
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    • v.62 no.5
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    • pp.358-363
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    • 2018
  • The purpose of this study is to show the possibility of using Cu catalyst in removal of $NO_x$ from automobile exhaust which is regarded as the primary source of fine dust PM2.5. The energy and the bond lengths of the three possible structures of Cu-NO complex, which is formed by binding NO molecule to Cu, and the changes in IR and Raman spectra are calculated using MPW1PW91 method on the level of 6-311(+)G(d,p) of basis sets with Gaussian 09 program. As a result, the enthalpy of formation of the Cu-NO complexes are obtained as ${\Delta}H=104.89$, 91.98, -127.48 kJ/mol for the linear, bent, and bridging forms of them, respectively. And the bond lengths between N and O in NO complexes, which becomes longer than NO molecule, indicates that O is easily reduced from Cu-NO. In addition, the Cu-NO complexes using Cu catalyst can be easily measured by infrared or Raman spectroscopy because in the IR and Raman spectra of the NO and Cu-NO complexes the positon and the intensity of bands are definitely different in each vibration mode.

Characterization of Silica Sol Particle Prepared by Sol-Gel Reaction from Sodium Silicate Solution (소디움실리케이트 수용액(水溶液)으로부터 솔-젤 반응(反應)에 의해 제조(製造)된 실리카 솔 입자특성(粒子特性) 고찰(考察))

  • Kim, Chul-Joo;Kim, Sung-Don;Jang, Hee-Dong;Yoon, Ho-Sung
    • Resources Recycling
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    • v.18 no.6
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    • pp.30-37
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    • 2009
  • Silica sol was prepared from the mixture of sodium silicate solution and oxidized silicate solution in which sodium had been removed by sol-gel process. The properties of sodium silicate solution and silicate solution thus prepared were characterized by yellow silicomolydate method. Moreover, the formation and growth of silica sol from sodium silicate solution was investigated. Sodium silicate solution with 2% of $SiO_2$ contains 95% of reactive silicate, and 50% of reactive silicate participates sol-gel reaction. From the results of FT-IR analysis, it was found that the intensity of silanol bond decreased and the intensity of siloxane bond increased with increasing reaction temperature. Zeta potential of silica sol prepared at each condition was -40~-60 mV and it could be known that silica sol in this study was well dispersed. The silica sol with 5~10 nm size could be prepared by heating the mixed solution of sodium silicate and silicate solution. And the silica sol grew into about 20 nm as silicate solution was added to silica sol solution.

Macro and Micro-electrochemical Characteristics on Dissimilar Welding Metal of Double Wall Gas Pipe for Duel Fuel Engine (이중 연료 엔진용 이중벽 가스 배관 이종 용접부의 매크로 및 마이크로 전기화학적 특성)

  • Kim, Seong-Jong;Park, Jae-Cheul;Han, Min-Su;Jang, Seok-Ki
    • Corrosion Science and Technology
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    • v.9 no.6
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    • pp.331-337
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    • 2010
  • This study compared the macro and micro electrochemical characteristics at the local area of welding metal on dissimilar welding parts for type 304 stainless steel (SS) and type 316L SS. The materials are used for double wall gas pipe of duel fuel engine for a ship. The various potentiodynamic experiments were performed several times in 10% ${H_2C_2O_2}{\cdot}{H_2O}$ solution using macro and micro methods, respectively. The micro electrochemical experiments conducted to resolve at local area on cross-section of dissimilar welding materials by micro-droplet cell device. The micro-droplet cell techniques can be used almost electrochemical experiments to resolve corrosion characteristics of the limited electrode area of the metallic surface between wetted spot of working electrode and tip of sharpened capillary tube. The results of macro electrochemical experiments show that resistance of active dissolution reaction at welding zone was high due to low current density by formation of passivation protection film at passive region. According to the micro electrochemical experiment, the corrosion current density of welding zone and bond zone were relatively high.

Inactivation of the DevS Histidine Kinase of Mycobacterium smegmatis by the Formation of the Intersubunit Disulfide Bond (Subunit 간의 disulfide 결합 형성에 의한 Mycobacterium smegmatis DevS histidine kinase의 불활성화)

  • Lee, Jin-Mok;Park, Kwang-Jin;Kim, Min-Ju;Ko, In-Jeong;Oh, Jeong-Il
    • Journal of Life Science
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    • v.20 no.6
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    • pp.853-860
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    • 2010
  • The DevSR two-component system is a major regulatory system involved in redox sensing in Mycobacterium smegmatis. The DevSR system consists of the DevS histidine kinase and its cognate DevR response regulator. When exposed to hypoxic conditions, the DevS histidine kinase is activated to phosphorylate the DevR response regulator, leading to the transcriptional activation of the DevR regulation. The ligand-binding state of the heme embedded in the N-terminal GAF domain of DevS determines the kinase activity of DevS. In this study, we demonstrated that the redox-responsive cysteine (C547) in the C-terminal kinase domain is involved in the redox-dependent control of DevS kinase activity. The formation of an intersubunit disulfide bond between the C547 residues in the presence of $O_2$ led to inactivation of DevS kinase activity. The reduction of the oxidized DevS with reductants such as $\beta$-mercaptoethanol and dithiothreitol resulted in the restoration of DevS kinase activity. It was demonstrated in vivo by complementation test that the substitution of C547 to alanine partially impaired the sensory function of DevS in M. smegmatis.

Theoretical Studies on the Diels-Alder Reactions between Cyclopentadiene and Conformationally Flexible Dienophiles (시클로 펜타디엔과 구조적으로 회전이 쉬운 Dienophile간의 Diels-Alder 반응에 대한 이론적 연구)

  • Kim, Chan Kyung;Lee, In Young;Lee, Bon Su;Lee, Ik Choon;Kim, Kwan Soo;Joo, Young Hyup
    • Journal of the Korean Chemical Society
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    • v.40 no.7
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    • pp.483-491
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    • 1996
  • Dieis-Alder reaction between cyclopentadiene and 5-membered ring compounds which have exo-cyclic double bond has been studied using the PM3 method. Transition states do not show large geometrical change with the variation of dienophiles. Two isomers are possible due to the rotation of the exo-cyclic double bond of a dienophile. The reactivity for the formation of different products are explained using the FMO energy gap. The exo and endo selectivity of the reaction has been also studied from the correlation between the deformation energy and the activation barrier. Minimum energy reaction path is discussed using the Curtin-Hammett principle.

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Enzymatic Characterization and Comparison of Two Steroid Hydroxylases CYP154C3-1 and CYP154C3-2 from Streptomyces Species

  • Subedi, Pradeep;Kim, Ki-Hwa;Hong, Young-Soo;Lee, Joo-Ho;Oh, Tae-Jin
    • Journal of Microbiology and Biotechnology
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    • v.31 no.3
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    • pp.464-474
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    • 2021
  • Bacterial cytochrome P450 (CYP) enzymes are responsible for the hydroxylation of diverse endogenous substances with a heme molecule used as a cofactor. This study characterized two CYP154C3 proteins from Streptomyces sp. W2061 (CYP154C3-1) and Streptomyces sp. KCCM40643 (CYP154C3-2). The enzymatic activity assays of both CYPs conducted using heterologous redox partners' putidaredoxin and putidaredoxin reductase showed substrate flexibility with different steroids and exhibited interesting product formation patterns. The enzymatic characterization revealed good activity over a pH range of 7.0 to 7.8 and the optimal temperature range for activity was 30 to 37℃. The major product was the C16-hydroxylated product and the kinetic profiles and patterns of the generated hydroxylated products differed between the two enzymes. Both enzymes showed a higher affinity toward progesterone, with CYP154C3-1 demonstrating slightly higher activity than CYP154C3-2 for most of the substrates. Oxidizing agents (diacetoxyiodo) benzene (PIDA) and hydrogen peroxide (H2O2) were also utilized to actively support the redox reactions, with optimum conversion achieved at concentrations of 3 mM and 65 mM, respectively. The oxidizing agents affected the product distribution, influencing the type and selectivity of the CYP-catalyzed reaction. Additionally, CYP154C3s also catalyzed the C-C bond cleavage of steroids. Therefore, CYP154C3s may be a good candidate for the production of modified steroids for various biological uses.

Improving wettability of polyethylene(PE) surface by ion assisted reaction (이온보조반응법에 의한 Polyethylene(PE) 표면의 친수성 증가)

  • 석진우;최성창;장홍규;정형진;최원국;고석근
    • Journal of the Korean Vacuum Society
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    • v.6 no.3
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    • pp.200-205
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    • 1997
  • Surface of polyethylene film was modified by ion assisted reaction in which ion beam is irradiated on polymer in reactive gas environments. Ion (argon and oxygen) beam energy was 1 keV, doses were varied from $1{\times}10^{14}$ to $1{\times}10^{17}$ inons/ $\textrm{cm}^2$, and amount of blowing oxygen from 0 to 4 sccm(ml/min). Wettability was measured by water contact angle measurement, and the surface functionality was analyzed by x-ray photoelectron spectroscopy. The contact angles of water to polyethylene modified by oxygen ion beam only decrease from 95 to degrees, and surface energy was not changed much. The contact angles remarkably decrease to 28 degrees and surface energy increase to 67 erg/ $\textrm{cm}^2$ when the films were modified by argon ion with various ion doses with blowing oxygen gases near the polyethylene surface. Improvement of wettability and surface energy are mainly due to the new functional group formation such as C-O or C=O, which are known as hydrophilic groups from the XPS analysis, and the assisted reaction is very effective to attach oxygen atoms to form functional groups on C-C bond chains of polyethylene.

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Mineralogy and Geochemistry of Green-colored Cr-bearing Sericite from Hydrothermal Alteration Zone of the Narim Gold Deposit, Korea (나림 금광상의 열수변질대에서 산출되는 녹색크롬-견운모의 광물학적 및 지구화학적 특징)

  • Lee, Hyun Koo;Lee, Chan Hee
    • Economic and Environmental Geology
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    • v.30 no.4
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    • pp.279-289
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    • 1997
  • Dark to pale green-colored, Cr-bearing sericites from hydrothermal alteration zone of the Narim gold deposit were investigated mineralogically and geochemically. The alteration zone is composed mineralogically of quartz, carbonate minerals and green sericite with minor amounts of chlorite, barite and sulfide minerals (pyrite, sphalerite, galena). The zone is enriched in As (967 to 1520 ppm), Cu (31 to 289 ppm), Ni (1027 to 1205 ppm), Pb (0.20 to 1.24 wt.%) and Zn (1.03 to 1.07 wt. %) compared with fresh rocks such as granitic gneiss, porphyritic biotite granite and basic dyke. The Cr, probably the chromophore element, is highly enriched in the alteration zone (1140 to 1500 ppm), host granitic gneiss (1200 ppm) and porphyritic biotite granite (1200 ppm). Occurrence and grain size of sericite are diverse, but most of the Cr-bearing sericites (150 to $200{\mu}m$ long and 20 to $30{\mu}m$ wide) occur along the boundaries between ore veins and host rocks (especially basic dyke and granitic gneiss). X-ray diffraction data of the sericite show its monoclinic form with unit-cell parameters of $a=5.202{\AA}$, $b=8.994{\AA}$, $c=20.103{\AA}$, ${\beta}=95.746^{\circ}$ and $V=935.83{\AA}^3$, which are similar with the normal 2M1-type muscovite. Representative chemical formula of the sericite is ($K_{1.54}Ca_{0.03}Na_{0.01}$)($Al_{3.42}Mg_{0.38}Cr_{0.14}Fe_{0.06}V_{0.02}$)($Si_{6.69}Al_{1.31}$)$O_{20}(OH)_4$. The Cr content increases with decrease of the octahedral Al content, and ranges from 0.36 to 2.58 wt.%. DTA and TG curves of the sericite show endothermic peaks at $342^{\circ}$ to $510^{\circ}$, $716^{\circ}$ to $853^{\circ}$ and $1021^{\circ}C$, which are due to the expulsion of hydroxyl group. The total weight loss by heating is measured to be about 8.8 wt. %, especially at $730^{\circ}C$. Infrared absorption experiments of the sericite show broad absorption band due to the O-H bond stretching vibration near the $3625cm^{-1}$, coupled with the 825 and $750cm^{-1}$ doublet. The vibration bands related with the H-O-Al and Si-O-Al bonds occur at $1030cm^{-1}$ and 500 to $700cm^{-1}$, respectively. Based on paragonite content of the sericite, the formation temperature of the Narim gold deposit is calculated to be $220{\pm}10^{\circ}C$.

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