• Title/Summary/Keyword: cross-linked bond

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A Novel Synthetic Route to Highly Cross-Linked Poly(alkylvinylether)s. Synthesis and Free Radical Polymerization of a Vinyl Ether Monomer Containing Electron Acceptors in Side Chain

  • 이주연;이현주;김무용
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.257-262
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    • 1996
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile 2 and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate 3 was prepared by the condensation of p-(2-vinyloxyethoxy)benzaldehyde 1 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2 and 3 polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃. The trisubstituted terminal double bond participated in the vinyl polymerization and radical polymerization of 2 and 3 led to swelling polymers 4 and 5 that were not soluble in common solvents due to cross-linking. Under the same polymerization conditions ethylvinyl ether polymerized well with model compounds of p-methoxybenzylidenemalononitrile 6 and methyl p-methoxybenzylidenecyanoacetate 7, respectively, to give 1:1 alternating copolymers 8 and 9 in high yields. Polymers 4 and 5 showed a thermal stability up to 300 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 8 and 9 were soluble in common solvents such as acetone and DMSO, and the inherent viscosities of the polymers were in the range of 0.36-0.74 dL/g. Films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 59-60 ℃.

A Theory for the Helix/Coil Transition of Oligopeptide Chain Dimer (올리고펩티드 사슬이합체의 헬릭스-코일 전이 이론)

  • Kim, Younggu;Pak, Hyungsuk
    • Journal of the Korean Chemical Society
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    • v.39 no.10
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    • pp.776-782
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    • 1995
  • A theory of the helix/coil transition for $\alpha$ helical dimer such as $\alpha$ tropomycin and paramycin is developed. The treatment differs from those formulated previously for oligopeptide dimer which is explained by the matrix method using Zimm-Bragg parameter: In the present treatement, it is explained by the zipper model which can account for the dangling H-bond. We calculate the fractional helicity in $\alpha$ helical dimer as a function of helix initiation $constant(\sigma)$, helix stability constant(${\xi}$) and hydrophobic interaction parameter(w). For $\alpha$ tropomycin, the helix stability profile is also calculated. The transitions of this oligomer due to the change of temperature and the concentration of oligopeptide involve simultaneous dissociation of the dimer. The transitions of dimers which have cross-linked S-S bonds or have long chains don't occur, because they keep always helical structures. The transitons due to the concentration of the oligopeptides are steeper than those due to the chain length or temperature.

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Bio-Derived Poly(${\gamma}$-Glutamic Acid) Nanogels as Controlled Anticancer Drug Delivery Carriers

  • Bae, Hee Ho;Cho, Mi Young;Hong, Ji Hyeon;Poo, Haryoung;Sung, Moon-Hee;Lim, Yong Taik
    • Journal of Microbiology and Biotechnology
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    • v.22 no.12
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    • pp.1782-1789
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    • 2012
  • We have developed a novel type of polymer nanogel loaded with anticancer drug based on bio-derived poly(${\gamma}$-glutamic acid) (${\gamma}$-PGA). ${\gamma}$-PGA is a highly anionic polymer that is synthesized naturally by microbial species, most prominently in various bacilli, and has been shown to have excellent biocompatibility. Thiolated ${\gamma}$-PGA was synthesized by covalent coupling between the carboxyl groups of ${\gamma}$-PGA and the primary amine group of cysteamine. Doxorubicin (Dox)-loaded ${\gamma}$-PGA nanogels were fabricated using the following steps: (1) an ionic nanocomplex was formed between thiolated ${\gamma}$-PGA as the negative charge component, and Dox as the positive charge component; (2) addition of poly(ethylene glycol) (PEG) induced hydrogen-bond interactions between thiol groups of thiolated ${\gamma}$-PGA and hydroxyl groups of PEG, resulting in the nanocomplex; and (3) disulfide crosslinked ${\gamma}$-PGA nanogels were fabricated by ultrasonication. The average size and surface charge of Dox-loaded disulfide cross-linked ${\gamma}$-PGA nanogels in aqueous solution were $136.3{\pm}37.6$ nm and $-32.5{\pm}5.3$ mV, respectively. The loading amount of Dox was approximately 38.7 ${\mu}g$ per mg of ${\gamma}$-PGA nanogel. The Dox-loaded disulfide cross-linked ${\gamma}$-PGA nanogels showed controlled drug release behavior in the presence of reducing agents, glutathione (GSH) (1-10 mM). Through fluorescence microscopy and FACS, the cellular uptake of ${\gamma}$-PGA nanogels into breast cancer cells (MCF-7) was analyzed. The cytotoxic effect was evaluated using the MTT assay and was determined to be dependent on both the concentration and treatment time of ${\gamma}$-PGA nanogels. The bio-derived ${\gamma}$-PGA nanogels are expected to be a well-designed delivery carrier for controlled drug delivery applications.

Biochemical Characterization of Serine Proteases with Fibrinolytic Activity from Tenodera sinensis (Praying Mantis)

  • Kim, Yeong-Shik;Hahn, Bum-Soo;Cho, So-Yean;Chang, Il-Moo
    • Toxicological Research
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    • v.17
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    • pp.97-104
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    • 2001
  • Three types of proteases (MEF-1, MEF-2 and MEF-3) were purified from the egg cases of Ten-odera sinensis using ammonium sulfate fractionation, gel filtration on Bio-Gel P-60 and affinity chromatography on DEAE Affi-Gel blue gel. The proteases were assessed homogeneous by SDS-polyacrylamide gel electrophoresis and have molecular weight of 31,500, 32,900 and 35,600 Da, respectively. The N-terminal regions of the primary structure were compared and they were found to be different each other. MEFs readily digested the $A\alpha$ - and B$\beta$-chains of fibrinogen and more slowly the ${\gamma}$-chain. The action of the enzymes resulted in extensive hydrolysis of fibrinogen and fibrin, releasing a variety of fibrinopeptides. MEF-1 was inactivated by Cu$^{2+}$ and Zn$^{2+}$ and inhibited by PMSF and chymostatin. MEF-2 was inhibited by PMSF, TLCK. soybean trypsin inhibitor. MEF-3 was only inhibited by PMSF and chymostatin. Antiplasmin was not sensitive to MEF-1 but antithrombin III inhibited the enzymatic activity qf MEF-1. MEF-2 specifically bound to anti plasmin Among the chromogenic protease substrates, the most sensitive one to the hydrolysis of MEFs was benzoyl-Phe-Val-Arg-p-nitroanilide with maximal activity at pH 7.0 and 3$0^{\circ}C$. MEF-1 preferentially cleaved the oxidized B-chain of insulin between Leu15 and Tyr16. In contrast, MEF-2 specifically cleaved the peptide bond between Arg23 and Gly24. D-dimer concentrations increased on incubation of cross-linked fibrin with MEF-1, indicating the enzyme has a strong fibrinolytic activity.ity.

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Implications of yield penetration on confinement requirements of r.c. wall elements

  • Tastani, Souzana P.;Pantazopoulou, Stavroula J.
    • Earthquakes and Structures
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    • v.9 no.4
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    • pp.831-849
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    • 2015
  • Seismic-design procedures for walls require that the confinement in the critical (plastic hinge) regions should extend over a length in the compression zone of the cross section at the wall base where concrete strains in the Ultimate Limit State (ULS) exceed the limit of 0.0035. In a performance-based framework, confinement is linked to required curvature ductility so that the drift demand at the performance point of the structure for the design earthquake may be met. However, performance of flexural walls in the recent earthquakes in Chile (2010) and Christchurch (2011) indicates that the actual compression strains in the critical regions of many structural walls were higher than estimated, being responsible for several of the reported failures by toe crushing. In this study, the method of estimating the confined region and magnitude of compression strain demands in slender walls are revisited. The objective is to account for a newly identified kinematic interaction between the normal strains that arise in the compression zone, and the lumped rotations that occur at the other end of the wall base due to penetration of bar tension yielding into the supporting anchorage. Design charts estimating the amount of yield penetration in terms of the resulting lumped rotation at the wall base are used to quantify the increased demands for compression strain in the critical section. The estimated strain increase may exceed by more than 30% the base value estimated from the existing design expressions, which explains the frequently reported occurrence of toe crushing even in well confined slender walls under high drift demands. Example cases are included in the presentation to illustrate the behavioral parametric trends and implications in seismic design of walls.

Fabrications and Properties of Colorless Polyimide Films Depending on Various Heat Treatment Conditions via Crosslinkable Monomer (가교 가능한 단량체를 이용한 무색투명 폴리이미드 필름 제조와 다양한 열처리에 따른 성질)

  • Choi, Il-Hwan;Chang, Jin-Hae
    • Polymer(Korea)
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    • v.34 no.5
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    • pp.391-397
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    • 2010
  • Poly(amic acid)(PAA) was prepared by reaction of bicyclo(2,2,2)oct-7-ene-2,3,5,6-tetracarboxylicdianhydride(BTDA) containing double bond for crosslinking and bis[4-(3-aminophenoxy) phenyl] sulfone(BAPS) in N,N-dimethylacetamide(DMAc). The cast film of PAA was heat-treated at different temperatures to create polyimide(PI) films. With increasing thermal crosslinking temperatures from 250 to $350^{\circ}C$, the thermo-mechanical properties, degree of crosslinking, and optical transparency of the cross-linked PI were investigated. The maximum enhancement in the thermo-mechanical properties was observed at a heat treatment condition of $350^{\circ}C$. However, the optical transparency was found to be optimal for $250^{\circ}C$ heat treatment. The degree of crosslinking in NMR was determined to be 85% to 93% with increasing annealing temperature conditions from 250 to $350^{\circ}C$.

The Americanization of a Canadian National Icon Anne of Green Gables (캐나다의 국가적 아이콘 『빨강머리 앤』의 미국화)

  • Kang, Suk Jin
    • Journal of English Language & Literature
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    • v.54 no.4
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    • pp.561-577
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    • 2008
  • L.M. Montgomery's Anne of Green Gables is not only confidently labelled a Canadian classic but also placed as a national icon along with the moose, the beaver, and the Habs in Canada. Anne's 'Canadianness' is partly due to its location in the rural world of Prince Edward Island. The fictional Avonlea is described as the ideal space where Canadian spirit can interact with the personified surrounding landscapes through Celtic imagination. Additionally, the communal bond of Avonlea fully demonstrates Scottish Canadian identities. The Scottish national character of Avonlea is responsible for clannishness of the Cuthberts and the Lyndes. The disrespect to the French is also due to Scottish heritage in Avonlea. As an outsider Anne wants to be integrated into the community of Avonlea, and successfully adapts herself to the regional shared values. Meanwhile she partly challenges the strictness and rigidness of the born Canadian Avonlea residents. Despite its Canadian origin, Anne of Green Gables is accepted as part of the American canon of children's literature in the Unite States. The configuration of Anne as an American heroine is noticeable among American scholars: by relocating it to the US the female Bildungsroman in the nineteenth century America, a group of literary critics adapt Anne as an American girl for American readers. The heroine of Anne of Green Gables is linked to American novels such as Louisa May Alcott's Little Women, Kate Douglas Wiggin's Rebecca of Sunnybrook Farm and Gene Stratten Porter's A Girl of the Limberlost. Anne is even classified as another Caddie by American literary critics: Anne is placed at the center of Caddie Woodlawn Syndrome as another Wisconsin pioneer child. Canadian identity of Anne is intentionally excluded and Anne was reborn as an American girl in the U.S. In this context, Anne functions as a sign of nation and a site for cross-national identity formation.

Peel strength of denture liner to PMMA and polyamide: laser versus air-abrasion

  • Korkmaz, Fatih Mehmet;Bagis, Bora;Ozcan, Mutlu;Durkan, Rukiye;Turgut, Sedanur;Ates, Sabit Melih
    • The Journal of Advanced Prosthodontics
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    • v.5 no.3
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    • pp.287-295
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    • 2013
  • PURPOSE. This study investigated the effect of laser parameters and air-abrasion on the peel strength of silicon-based soft denture liner to different denture resins. MATERIALS AND METHODS. Specimens (N=180) were prepared out of three different denture base resins (Rodex, cross-linked denture base acrylic resin; Paladent, heat-cured acrylic resin; Deflex, Polyamide resin) ($75mm{\times}25mm{\times}3mm$). A silicon-based soft denture liner (Molloplast B) was applied to the denture resins after the following conditioning methods: a) Air-abrasion ($50{\mu}m$), b) Er,Cr:YSGG laser (Waterlase MD Turbo, Biolase Technology) at 2 W-20 Hz, c) Er,Cr:YSGG laser at 2 W-30 Hz, d) Er,Cr:YSGG laser at 3 W-20 Hz, e) Er,Cr:YSGG laser at 3 W-30 Hz. Non-conditioned group acted as the control group. Peel test was performed in a universal testing machine. Failure modes were evaluated visually. Data were analyzed using two-way ANOVA and Tukey's test (${\alpha}$=.05). RESULTS. Denture liner tested showed increased peel strength after laser treatment with different parameters ($3.9{\pm}0.4-5.58{\pm}0.6$ MPa) compared to the control ($3.64{\pm}0.5-4.58{\pm}0.5$ MPa) and air-abraded groups ($3.1{\pm}0.6-4.46{\pm}0.3$ MPa), but the results were not statistically significant except for Paladent, with the pretreatment of Er,Cr:YSGG laser at 3 W-20 Hz. Polyamide resin after air-abrasion showed significantly lower peel strength than those of other groups ($3.1{\pm}0.6$ MPa). CONCLUSION. Heat-cured acrylic resin, PMMA, may benefit from Er,Cr:YSGG laser treatment at 3 W-20 Hz irradiation. Air-abrasion of polyamide resins should be avoided not to impair their peel bond strengths to silicon-based soft denture liners.

The Effect of Acetonitrile on the Texture Properties of Sodium Silicate Based Silica Aerogels (아세토니트릴 첨가가 물유리 기반 실리카 에어로겔의 기공구조에 미치는 영향)

  • Kim, Younghun;Kim, Taehee;Shim, Jong Gil;Park, Hyung-Ho
    • Journal of the Microelectronics and Packaging Society
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    • v.25 no.4
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    • pp.143-148
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    • 2018
  • Sodium silicate based silica aerogels are lower in cost than silica alkoxide based silica aerogels, but the demand is decreasing as their physical properties are lowered. In this research, acetonitrile as a drying control chemical additive (DCCA) is added in the sol state to improve the pore-structural properties of sodium silicate based silica aerogel by preventing the agglomeration of particles and cross-linked bond. The sodium silicate based silica aerogel by ambient pressure drying were prepared by sol-gel process. Acetonitrile/$Na_2SiO_3$ molar ratio of 0, 0.05, 0.1, 0.15, and 0.2 was added to the sol state. The physical properties of the final product were analyzed using Fourier transform infrared, contact angle measurement, Brunauer-Emmett-Teller and Barrett-Joyner-Halenda measurements and field emission scanning electron microscopy. It was confirmed that the sample with adding 0.15 molar ratio of acetonitrile and sodium silicate showed a high specific surface area ($577m^2/g$), a high pore volume (3.29 cc/g), and a high porosity (93%) comparable to the pore-structural properties of silica alkoxide based silica aerogels.