• Title/Summary/Keyword: in-group bonds

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Redistribution/Dehydrocoupling of Endocrine n-$Bu_3SnH$ to Polystannanes Catalyzed by Group 4 Metallocene Complexes

  • Park, Jaeyoung;Kim, Seongsim;Lee, Beomgi;Cheong, Hyeonsook;Noh, Ji Eun;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.5 no.2
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    • pp.79-83
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    • 2012
  • Trialkyltin n-$Bu_3SnH$, an endocrine disruptor, was slowly converted by the catalytic action of group 4 $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) to produce two phases of products: one is an insoluble cross-linked solid, polystannane in 7-23% yield as minor product via redistribution/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 69-90% yield as major product via simple dehydrocoupling process. Redistribution/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, leading to an insoluble polystannane. This is the first exciting example of redistribution/dehydrocoupling of a tertiary hydrostannane catalyzed by early transition metallocenes.

Photo-Induced Cationic Ring-Opening Polymerization of 4-Methylene-2-styryl-1,3-dioxolane by Benzylsulfonium Salt

  • Park, Jaekyeung
    • Macromolecular Research
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    • v.9 no.4
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    • pp.206-209
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    • 2001
  • One of the approaches to obtain functional polymer is polymerization of a monomer having two functional groups. Although polymerization of a monomer having two different types of functional group is general, the author has been interested in the polymerization of a monomer having two similar types of functional group. This work shows the preparation and selective polymerization of 4-methylene-2-styryl-1,3-dioxolane having two similar reactive double bonds via cationic polymerization at ambient temperature. Cationic ring-opening polymerization of 4-methylene-2-styryl-1,3-dioxolane using benzylsulfonium salt as a photo-initiator quantitatively afforded high molecular weight of poly(keto-ether).

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Influence of Polycondensation Type on Structure of Resorcinol Formaldehyde Resin Studied by Molecular Simulation

  • Park, Sung-Seen
    • Macromolecular Research
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    • v.8 no.3
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    • pp.125-130
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    • 2000
  • Resorcinol formaldehyde resins are synthesized by polycondensation of resorcinol with formal-dehyde and have various structures by the condensation type. The influence of polycondensation type on the stability and structure of the resorcinol formaldehyde resin was studied by molecular mechanics and molecular dynamics. The resins formed by 2,6-polycondensation and 4,6-polycondensationwith head-to-tail orientations have structures of intramolecular hydrogen bonds between 1-hydroxyl groups and between outer hydroxyl groups of the adjacent resorcinols, respectively. The resin formed by 2,6-polycon-densation with head-to-head orientation has a structure that inner hydroxyl groups cluster in the center of the molecule. Energetical stability of the resin is affected by both the intramolecular hydrogen bonds and the steric' hindrance by phenyl group.

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Redistribution/Dehydrocoupling of Tertiary Alkylstannane $n-Bu_3 SnH$ Catalyzed by Group 4 and 6 transition Metal Complexes

  • 우희권;송선정;김보혜
    • Bulletin of the Korean Chemical Society
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    • v.19 no.11
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    • pp.1161-1164
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    • 1998
  • The catalytic transformation of sterically bulky tertiary stannane n-Bu3SnH by the Cp2MCl2/Red-Al (M=Ti, Zr, Hf) and M(CO)6 (M=Cr, Mo, W) catalysts yielded two kinds of catenated products: one is a cross-linked polystannane as minor product, and the other is hexabutyldistannane (n-Bu3Sn)2 as major product. The distannane was produced by simple dehydrocoupling of n-Bu3SnH, whereas the cross-linked polystannane could be obtained via redistribution/dehydrocoupling combination process of n-Bu3SnH. The redistribution/dehydrocoupling combination process may initially produce a low-molecular-weight oligostannane with partial backbone Sn-H bonds which could then undergo an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane.

Gelation Properties and Industrial Application of Functional Protein from Fish Muscle-1. Effect of pH on Chemical Bonds during Thermal Denaturation (기능성 어육단백질의 젤화 특성과 산업적 응용-1. 가열변성 중 화학결합에 미치는 pH의 영향)

  • Jung, Chun-Hee;Kim, Jin-Soo;Jin, Sang-Keun;Kim, Il-Suk;Jung, Kyoo-Jin;Choi, Yeung-Joon
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.33 no.10
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    • pp.1668-1675
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    • 2004
  • The effect of pH on surface hydrophobicity, sulfhydryl group, infrared spectrum, SDS-PAGE (sodium dodecyl sulfate-polyacrylamide gel electrophoresis) pattern and enthalpy was investigated in recovered protein from mackerel and frozen blackspotted croaker by alkaline processing. Hydrophobic residue in myofibrillar protein exposed to the surface of protein, and hydrophobic interaction were the highest around 6$0^{\circ}C$. The surface hydrophobicity was different between myofibrillar protein and myofibrillar protein including sarcoplasmic protein (recovered protein). The peak at 1636 c $m^{-l}$ was increased with pH, and the recovered protein was unfolded in alkali pH. Difference of surface and total sulfhydryl group at pH 7.0 and 10 was comparative high, and decrease of surface sulfhydryl group indicated formation of S-S bonds. Mackerel and frozen blackspotted croaker in alkaline pH showed bands of polymerized myosin heavy chain on SDS-PAGE pattern. The transition temperatures of recovered protein were 33.1, 44.3 and 65.5$^{\circ}C$. Gelation of recovered protein from alkali processing was estimated by increase of $\beta$-sheet structure by pH treatment, S-S bonds by oxidation of surface sulfhydryl group in heating, polymerization of myosin heavy chain in order.r.

The Crystal and Molecular Structure of p-Phenylenediamine Dihydroperchlorate (p-Phenylenediamine Dihydroperchlorate의 결정 및 분자구조)

  • Ahn Choong Tai
    • Journal of the Korean Chemical Society
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    • v.21 no.5
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    • pp.320-329
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    • 1977
  • p-Phenylenediamine dihydroperchlorate, $C_6H_4N_2H_4{\cdot}2HC1O_4$, crystallizes in space group $P\={1}$ with $a=4.79{\pm}0.02,\;b=9.03{\pm}0.02,\;c=7.12{\pm}0.03{\AA},\;{\alpha}=109.4{\pm}0.2,\;{\beta}=79.6{\pm}0.2,\;r=104.6{\pm}0.2^{\circ},\;Z=1$. The structure has been solved by the Patterson and Fourier methods. The refinement by block-diagonal least-squares cycles gives R = 0.13 for 387 observed reflexions collected on equi-inclination Weissenberg photographs with CuK${\alpha}$ radiation. There are two different types of five hydrogen bonds. The first type consists of one trifurcated N${\cdot}{\cdot}{\cdot}$O hydrogen bond and the second of two normal N${\cdot}{\cdot}{\cdot}$O hydrogen bonds, both of which exist between the amino group and the perchlorate, groups. A p-phenylenediamine group is approximately planar within an experimental error and bonded to twelve perchlorates: ten perchlorates forming hydrogen bonds and two being contacted with the van der Waals forces. A perchlorate group is surrounded by six p-phenylenediamines and four perchlorates; among the six p-phenylenediamines, five of them are hydrogen-bonded, and the rest contacted with the van der Waals force.ce anaysis of our samples and investigated the variarions in the values of parameters obtained through fitting the theoretical impedance to the experimental impedance. The characters of the dielectric constant and the impedance showed abnormal variations for the 0.2 at K-doped NSBN ceramics, which we were able to interpret in terms of the variations in the number A-site vacancies with the K doping ratio. From these results, A-site vacancies are thought to be space charges that influence the ferroelectric properties of NSBN ceramics.

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Bonding Performance of Maltodextrin and Citric Acid for Particleboard Made From Nipa Fronds

  • Santoso, Mahdi;Widyorini, Ragil;Prayitno, Tibertius Agus;Sulistyo, Joko
    • Journal of the Korean Wood Science and Technology
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    • v.45 no.4
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    • pp.432-443
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    • 2017
  • Maltodextrin and citric acid are two types of natural materials with the potential as an eco-friendly binder. Maltodextrin is a natural substance rich in hydroxyl groups and can form hydrogen bonds with lignoselulosic material, while citric acid is a polycarboxylic acid which can form an ester bond with a hydroxyl group at lignoselulosic material. The combination of maltodextrin and citric acid as a natural binder materials supposed to be increase the ester bonds formed within the particleboard. This research determined to investigate the bonding properties of a new adhesive composed of maltodextrin/citric acid for nipa frond particleboard. Maltodextrin and citric acid were dissolved in distillated water at the ratios of 100/0, 87.5/12.5, 75/25 and 0/100, and the concentration of the solution was adjusted to 50% for maltodextrin and 60% citric acid (wt%). This adhesive solution was sprayed onto the particles at 20% resin content based on the weight of oven dried particles. Particleboards with a size of $25{\times}25{\times}1cm$, a target density $800kg/m^3$ were prepared by hot-pressing at press temperatures of $180^{\circ}C$ or $200^{\circ}C$, a press time of 10 minute and board pressure 3.6 MPa. Physical and mechanical properties of particleboard were tested by a standard method (JIS A 5908). The results showed that added citric acid level in maltodextrin/citric acid composition and hot-pressing temperature had affected to the properties of particleboard. The optimum properties of the board were achieved at a pressing temperature of $180^{\circ}C$ and the addition of only 20% citric acid. The results also indicated that the peak intensity of C=O group increased and OH group decreased with the addition of citric acid and an increase in the pressing temperature, suggesting an interreaction between the hydroxyl groups from the lignocellulosic materials and carboxyl groups from citric acid to form the ester groups.

Investigation of Changes in Structural Characteristics and Chemical Composition after Heat Treatment Process of JIS-SUJ2 Bearing Steel (JIS-SUJ2 베어링강의 열처리 이후 표면 및 심부에서 나타나는 구조적, 화학적 물성 변화)

  • Donghee Lee;Kyun Taek Cho;Hyeonmin Yim;Seung-Hwan Oh;Tae Bum Kim;Woo-Byoung Kim
    • Korean Journal of Materials Research
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    • v.33 no.12
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    • pp.558-564
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    • 2023
  • In this study, we designed and manufactured a large angular contact ball bearing (LACBB) with low deformation using JIS-SUJ2 steel and analyzed changes in its structural characteristics and chemical composition upon heat treatment. The bearing was produced by hot forging and heat treatment including a quenching and tempering (Q/T) process, and its properties were analyzed using 4 mm thick specimens. A difference in the size distribution of the carbide in the outer and inner parts of the bearing was observed and it was confirmed that large and non-uniform carbide was distributed in the inner part of the bearing. After heat treatment, the hardness value of the outer part increased from 13.4 HRC to 61 HRC and the inner part increased from 8.0 HRC to 59.7 HRC. As a result of X-ray diffraction (XRD) measurements, the volume fraction of the retained austenite contained in the outer part was calculated to be 3.5~4.8 % and the inner part was calculated to be 3.6~5.0 %. The surface chemical composition and the content of chemical bonds were quantified through X-ray photoelectron spectroscopy (XPS), and a decrease in C=C bonds and an increase in Fe-C bonds were confirmed.

Identification of a Mature form and Characterization of Thermostability of a Serine-type Protease from Aquifex pyrophilus

  • Kim, Yun-Kyeong;Choi, In-Geol;Nam, Won-Woo;Yu, Yeon-Gyu
    • BMB Reports
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    • v.33 no.6
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    • pp.493-498
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    • 2000
  • Aquifex pyrophilus, a hyperthermophilic bacterium, has a serine-type protease that is located at the cell wall fraction with a mature size of 43 kDa. Molecular cloning of the protease gene revealed that it has an ORF of 619 amino acids with homologous catalytic site of serine-type proteases [Choi, I.-G., Bang, W.-K., Kim, S.-H., Yu, G. Y., J. Biol. Chem. (1999), Vol. 274, pp. 881-888]. Constructs containing different regions of the protease gene, including a alanine-substituted mutant at the active site serine, were constructed, and the factors affecting the expression level of the cloned protease gene in E. coli were examined. The presence of the C-terminus hydrophobic region of the protease hindered over-expression in E. coli. Also, the proteolytic activity of the expressed protein appeared to toxic to E. coli. An inactive form that deleted both of the N-terminal signal sequence and the C-terminal polar residues was over-expressed in a soluble form, purified to homogeneity, and its thermostability examined. The purified protein showed three disulfide bonds and three free sulfhydryl group. The thermal denaturation temperature of the protein was measured around $90^{\circ}C$ using a differential scanning calorimeter and circular dichroism spectrometry. The disulfide bonds were hardly reduced in the presence of reducing agents, suggesting that these disulfide bonds were located inside of the protein surface.

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The Crystal Structure of One Natural Compound Cyclo-(1,10-Docandiamino-11,20-Docanedioic) Amide (1,12-Diazacyclodocosane-2,11-Dione)

  • Wei, Wan-Xing;Pan, Yuan-Jiang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.11
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    • pp.1527-1530
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    • 2002
  • 1,12-diazacyclodocosane-2,11-dione was first isolated from a plant Phyllanthus niruri Linn. Its structure has been determined by means of spectroscopy methods and X-ray crystallography. Two peptide groups in the big ring (lactam) are the main factors influencing intermolecular contacts. The hydrogen-bond interaction of these hydrophilic groups is observed in the crystal structure. Meanwhile, C-H···O hydrogen bonds in molecules contribute to the formation of the whole crystal. These two kinds of hydrogen-bond form six- member rings among molecules. This compound crystallizes in the triclinic space group P-1 with a= 9.588(1) $\AA$, b= $9.850(1)\AA$, c = $11.810(1)\AA$, $\alpha=$ 68.18(1)$^{\circ}C$ , $\beta=$ 84.98(1), $\gamma$ = 86.03(1)$^{\circ}C$ , V = $1030.66(17)\AA3$ , Z = 2. A disorder of five-member carbon chain in the whole ring is observed in the title compound. The bond angle 105.8(4) is determined for a extreme configuration C(14)-C(15)-C(16), and 117.7(10) for another extreme configuration C(14')-C(15')-C(16'). In this crystal, two molecules are tied each other by short intermolecular hydrogen bonds, the oxygen atom being tied by hydrogen bond to nitrogen atom of another two molecules. The NMR and IR spectral data coincides to the structure of the compound.