• Title/Summary/Keyword: In-situ synthesis

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Synthesis and Micellar Characterization of CBABC Type PLGA-PEO-PPO-PEO-PLGA Pentablock Copolymers

  • Seong, Haseob;Cho, Eun-Bum;Oh, Joongseok;Chang, Taihyun
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2342-2348
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    • 2014
  • Poly(lactic-co-glycolic acid) (PLGA) were grafted to both ends of Pluronic$^{(R)}$ F68 ($(EO)_{75}(PO)_{30}(EO)_{75}$) triblock copolymer to produce poly{(lactic acid)$_m$-co-(glycolic acid)$_n$}-b-poly(ethylene oxide)$_{75}$-b-poly(propylene oxide)$_{30}$-b-poly(ethylene oxide)$_{75}$-b-poly{(lactic acid)$_m$-co-(glycolic acid)$_n$} (PLGA-F68-PLGA) pentablock copolymers. Molecular weights of PLGA blocks were controlled and five kinds of pentablock copolymers with different PLGA block lengths were synthesized using in-situ ring-opening polymerization of D,L-lactide and glycolide with tin(II) 2-ethylhexanoate ($Sn(Oct)_2$) catalyst. PLGA-F68-PLGA pentablock copolymers were characterized by $^1H$- and $^{13}C$-NMR, GPC, and TGA. The numbers (2m, 2n) of repeating units for lactic acid and glycolic acid inside PLGA segments were obtained as (48, 17), (90, 23), (125, 40), (180, 59), and (246, 64), with $^1H$-NMR measurement. From NMR data, the resultant molecular weights were determined in the range of 12,700-29,700, which were similar to those obtained from GPC. Polydispersity index was increased in the range of 1.32-1.91 as the content of PLGA blocks increased. TG and DTG thermograms showed discrete degradation traces for PLGA and F68 blocks, which indicate the weight fractions of PLGA blocks in pentablock copolymers can be calculated by TG profile and it is possible to remove PLGA block selectively. Hydrodynamic radius and radius of gyration of pentablock copolymer micelle were obtained in the range of 46-68 nm and 31-49 nm, respectively, in very dilute (i.e. 0.005 wt %) aqueous solution of THF:$H_2O$ = 10:90 by volume at $25^{\circ}C$.

Synthesis and Spectroscopic Investigations of Some New rganotelluronium alts Based on Dicyclohexyl Telluride (디시클로헥실 텔루르염에 기반한 유기텔루로늄염의 성과 분광학적 분석)

  • Al-Rubaie, Ali Z.;Al-Mudhaffar, Dhafir M. H.;Al-Mowali, Ali H.;Asker, Kahtan A.
    • Journal of the Korean Chemical Society
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    • v.53 no.5
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    • pp.530-535
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    • 2009
  • Dicyclohexyl telluride was obtained in a high yield by the reaction of cyclohexyl bromide with NaTeH(prepared in situ) in an aqueous ethanolic solution. A series of new organotelluronium salts of the general formula ${(cyclo-C_6H_11)}_2Te(R)X$ (where R = $CH_3$, X = I (1); R = $C_2H_5$, X = Br(2); R = $C_2H_5$, X = I (3); R = C_3H_5$, X = Br (4)) were prepared by the reaction of ${(cyclo-C_6H_11)}_2Te$ with the corresponding alkyl halide. Reaction of 1 with NaBPh4 gave compound 5 ( i.e. R = CH3, X = BPh4 ‒) in 78% yield. Reaction of ${(cyclo-C_6H_11)}_2Te$ with benzyl bromide and 4-bromophenacyl bromide gave unexpectedly dibenzylcyclohexyltelluronium bromide (6) and bis(4-bromophenacyl)cyclohexyltelluronium bromide (7), respectively. Reaction of 6 with NaBPh4 gave the corresponding tetraphenylborate derivative (8) in high yield. $^1H$ NMR studies revealed that in $CDCl_3$solution compound 1 eliminated alkyl halide. Conductivity, IR, $^1H\;and\;^{13}C$ NMR and thermal data for the new compounds are presented and discussed.

Stereoselective Synthesis of Novel Bestatin Analogs (새로운 베스타틴 유사체의 입체선택적 합성)

  • Seo, Youngran;Lee, SooBeom;Kim, Young Gyu
    • Applied Chemistry for Engineering
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    • v.26 no.1
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    • pp.111-115
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    • 2015
  • Two new analogs of bestatin were prepared from $\small{D}$-leucine and $\small{D}$-valine in a stereoselective and efficient way. An aminopeptidase inhibitor bestatin shows significant biological effects on immunomodulation and is marketed for the treatment of acute myelocytic leukemia. The key intermediates, trans-oxazolidine methyl esters 2a and 2b, were obtained with more than 20 to 1 stereoselectivity in a one-pot procedure by the three cascade reactions between N-hydroxymethyl protected ${\alpha}$-amino aldehydes (4a and 4b) and phenylsulfonylnitromethane ($PhSO_2CH_2NO_2$) and the following in-situ ozonolysis. Basic hydrolysis of 2a and 2b, and then the peptide coupling with $\small{L}$-Leu-OMe produced the protected derivatives of two new bestatin analogs, 3a and 3b, respectively. The new isobutyl and isopropyl analogs of bestatin (1a and 1b) were produced in overall 51% and 38% yields, respectively, with high stereoselectivity from the corresponding protected ${\alpha}$-amino aldehydes 4 in a six-step process.

A Study on the Commercialization of Polyamide 66/Polypropylene Blend (폴리아마이드 66/폴리프로필렌 블렌드의 상업화 연구)

  • Kim, Seog-Jun;Nam, Byeong-Uk
    • Elastomers and Composites
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    • v.38 no.3
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    • pp.262-272
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    • 2003
  • Maleic anhydride-grafted-polypropylene(PP-g-MA) were used as a blend component and a compatibilizer, respectively, for two reactive blends of polyamide 66(PA 66)PP-g-MA binary blends and PA 66/polypropylene(PP)/PP-g-MA ternary blends. The goal of this work was to investigate the property differences between binary and ternary blends. Tensile strength, flexural modulus, heat deflection temperature, impact strength, melt flow index, and the dependence of melt viscosity on the shear rate were examined. The impact strengths of binary blends were higher than those of ternary blends at all compositions, since the in situ synthesis of PP-g-PA 66 copolymer through the imide formation between the amine end group of PA 66 and the anhydride group of PP-g-MA gave the increase of molecular weight and was more popular in binary blends than in ternary blends. In case of ternary blends, most of the properties were superior to those of binary blends, owing to the better properties of PP compared with PP-g-MA. The toughened binary blends with 70/30(PA 66/PP-g-MA) and 80/20 ratios were not commercially applicable due to their poor processibility. So, the ternary blends which showed lower melt viscosities were recommended for the commercial applications.

Production and High Temperature Mechanical Properties of Ti-TiC Composite by Reaction Milling (반응밀링법에 의한 Ti-TiC 복합재료의 제조 및 고온 기계적 특성)

  • Jin, Sang-Bok;Choe, Cheol-Jin;Lee, Sang-Yun;Lee, Jun-Hui;Kim, Sun-Guk
    • Korean Journal of Materials Research
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    • v.8 no.10
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    • pp.918-924
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    • 1998
  • This study has been carried out to investigate the effect of reaction milling time on the synthesis of Ti- TiC p powder synthesised from the elemental titanium and activated carbon by reaction milling(RM), and the effect of vacu­u urn hot pressing temperature and TiC volume fraction on microstructural and mechanical properties of Ti- TiC com­p posite $\infty$ns이idated by vacuum hot pressing(VHP).T The elemental powders of titanium and activated carbon can be converted into Ti- TiC composite powders by reac­t tion milling for about 300hours, and were the average grain size of the as- milled powders has been measured to be a about $5\mu\textrm{m}$. The relative density of Ti- TiC VHPed above $1000^{\circ}C$ during Ihr is about 98% and the mechanical properties o of In- situ Ti- TiC composites are improved by TiC particle dispersed uniformly on titanium matrix. In order to investi­g gate thermal stability of Ti- TiC composite, after annealing at $600^{\circ}C$ for 80hrs micro- Vickers hardness have been per­f formed, and the values have been shown little changed as compared with those before annealing. The compact has b been tested on high temperature compressive test at $700^{\circ}C$ and has showed a high temperature compressive strength of 330MPa in a Ti- 20vol% TiC.

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Phase Transition Studies on BaTiO3 and PbTiO3 and Synthesis of Silicate Perovskite (BaTiO3와 PbTiO3에 대한 상(相)전이 연구와 규산염 페롭스카이트의 합성)

  • Kim, Young-Ho
    • Journal of the Mineralogical Society of Korea
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    • v.1 no.2
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    • pp.94-103
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    • 1988
  • Diamond anvil cell (DAC) interfaced with a YAG laser heating system has been used to study the phase transformations on perovskite structured titanates ($BaTiO_3$, and $PbTiO_3$) and to synthesize the silicate perovskite phase from the orthopyroxenes of $MgSiO_3$ and $(Mg_{0.87},\;Fe_{0.13})SiO_3$. $BaTiO_3$ and $PbTiO_3$ transform from tetragonal phase to cubic at the pressures of approximately 2.6 GPa and 4.0 GPa at room temperature, respectively. Cubic phases of the both show wide range of stability in the extended in-situ high pressures and high temperature regions. Starting orthoenstatite of $MgSiO_3$ has yielded the perovskite phase as the major structure with ilmenite, gamma-spinel, betta-spinel and stishovite phases at ~38 GPa and ${\sim}1,000^{\circ}C$. $(Mg_{0.87},\;Fe_{0.13})SiO_3$ has shown the perovskite as the major phase with betta-spinel, stishovite and enstatite phases at ~35 GPa and ${\sim}1,000^{\circ}C$. The ilmenite phase does not occur at this condition.

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Pervaporation of binary Water/Methanol and Water/Butanol Mixtures through Zeolite 4A Membranes: Experiments and Modeling (제올라이트 4A 분리막을 이용한 물/메탄올, 물/부탄올 혼합물의 투과증발 특성 연구: 실험 및 모형)

  • Oh, Woong-Jin;Jung, Jae-Chil;Yeo, Jeong-gu;Lee, Jung Hyun;Kim, Hyunuk;Park, Young Cheol;Lee, Dong-Ho;Moon, Jong-Ho;Cho, Churl-Hee
    • Membrane Journal
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    • v.27 no.6
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    • pp.487-498
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    • 2017
  • In this study, pervaporation performances of water/methanol and water/butanol mixture were evaluated using zeolite 4A membranes manufacutred by FINETECH by experimental works and numerical modeling. Permeation and separation characteristics, such as flux and separation factor, were analyzed by gas chromatography (TCD) and liquid nitrogen traps. Experiments have shown that water is selectively separated from a mixture of water and methanol (separation factor up to approximately 250) and water and butanol (separation factor up to approximately 1,500). Generalized Maxwell Stefan (GMS) theory was implemented to predict pervaporation behaviors of water/alcohol mixtures and diffusional coefficients of zeolite layer were obtained through parameter estimation using $MATLAB^{(R)}$ optimization toolbox. Since the pore size of zeolite 4A are much larger than kinetic diameter of water molecules and smaller than those of methanol and butanol, zeolite 4A membranes can be applied to in situ water removal process such as membrane reactors or hybrid reaction-dehydration process.

Analysis of the Amount of Telomeric DNA and Telomerase Activity on Preimplantation Mouse Embryoic Cells (마우스 수정란의 초기 배 발생단계별 Telomeric DNA의 양적 분석과 Telomerase 활성도 분석)

  • Kang M. Y.;Han M. S.;Lee S. C.;Kim J. H.;Sohn S. H.
    • Reproductive and Developmental Biology
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    • v.29 no.1
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    • pp.1-7
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    • 2005
  • Telomeres consisting of (TTAGGG)n tandem repeat DNA sequences and associated proteins are essential for chromosome stability and related with cell senescence, apoptosis and cancer. The telomerase is a ribonucleoprotein which act as a template for the synthesis of telomeric DNA. This study was carried out to identify the distribution of telomeres on mouse chromosomes and also to analyze the amount of telomeres and telomerase activity of mouse embryos at early embryonic stages. Germ cells and early embryos from 1 cell to blastocyst stage were analyzed. The amount of telomeres was analyzed by quantitative fluorescence in situ hybridization technique(Q-FISH) using a human telomeric DNA probe, and telomerase activity was measured by telomeric repeat amplification protocol assay(TRAP). In results, the telomeres on mouse chromosomes were distributed at the ends of all autosomes and sex chromosomes. Although the quantity of telomeres varied among chromosomes, most of chromosomes had higher amount in q-arm telomeres than in p-arm telomeres. The results of Q-FISH indicated that the relative amount of telomeres of mouse embryos in each embryonic stage was approximately the same except the higher amount in blastocysts. Using TRAP assay on mouse embryos, telomerase activity was detected in all preimplantation stages from mature oocytes to blastocysts. Especially the telomerase activity was significantly increased at the morula and blastocyst stage. In conclusion, there may be a close association between the amount of telomeres and telomerase activity in early embryonic stages, and analysis of telomere quantity and telomerase activity on early development will be helpful for the investigation of embryogenesis and embryonic cell differentiation in mice.

Preparation of Novel Natural Polymer-based Magnetic Hydrogels Reinforced with Hyperbranched Polyglycerol (HPG) Responsible for Enhanced Mechanical Properties (과분지 폴리글리세롤(HPG) 강화를 통해 기계적 물성이 향상된 새로운 천연 고분자 기반 자성 하이드로젤의 제조)

  • Eun-Hye Jang;Jisu Jang;Sehyun Kwon;Jeon-Hyun Park;Yujeong Jeong;Sungwook Chung
    • Clean Technology
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    • v.29 no.1
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    • pp.10-21
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    • 2023
  • Hydrogels that are made of natural polymer-based double networks have excellent biocompatibility, low cytotoxicity, and high water content, assuring that the material has the properties required for a variety of biomedical applications. However, hydrogels also have limitations due to their relatively weak mechanical properties. In this study, hydrogels based on an alginate di-aldehyde (ADA) and gelatin (Gel) double network that is reinforced with additional hydrogen bonds formed between the hydroxyl (-OH) groups of the hyperbranched polymer (HPG) and the functional groups present inside of the hydrogels were successfully synthesized. The enhanced mechanical properties of these synthesized hydrogels were evaluated by varying the amount of HPG added during the hydrogel synthesis from 0 to 25%. In addition, magnetite nanoparticles (Fe3O4 NPs) were synthesized within the hydrogels and the structures and the magnetic properties of the hydrogels were also characterized. The hydrogels that contained 15% HPG and Fe3O4 NPs exhibited superparamagnetic behaviors with a saturation magnetization value of 3.8 emu g-1. These particular hydrogels also had strengthened mechanical properties with a maximum compressive stress of 1.1 MPa at a strain of 67.4%. Magnetic hydrogels made with natural polymer-based double networks provide improved mechanical properties and have a significant potential for drug delivery and biomaterial application.

Lipopolysaccharide-induced Synthesis of IL-1beta, IL-6, TNF-alpha and TGF-beta by Peripheral Blood Mononuclear Cells (내독소에 의한 말초혈액 단핵구의 IL-1beta, IL-6, TNF-alpha와 TGF-beta 생성에 관한 연구)

  • Jung, Sung-Hwan;Park, Choon-Sik;Kim, Mi-Ho;Kim, Eun-Young;Chang, Hun-Soo;Ki, Shin-Young;Uh, Soo-Taek;Moon, Seung-Hyuk;Kim, Yang-Hoon;Lee, Hi-Bal
    • Tuberculosis and Respiratory Diseases
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    • v.45 no.4
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    • pp.846-860
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    • 1998
  • Background: Endotoxin (LPS : lipopolysaccharide), a potent activator of immune system, can induce acute and chronic inflammation through the production of cytokines by a variety of cells, such as monocytes, endothelial cells, lymphocytes, eosinophils, neutrophils and fibroblasts. LPS stimulate the mononucelar cells by two different pathway, the CD14 dependent and independent way, of which the former has been well documented, but not the latter. LPS binds to the LPS-binding protein (LBP), in serum, to make the LPS-LBP complex which interacts with CD14 molecules on the mononuclear cell surface in peripheral blood or is transported to the tissues. In case of high concentration of LPS, LPS can stimulate directly the macrophages without LBP. We investigated to detect the generation of proinflammatory cytokines such as interleukin 1 (IL-1), IL-6 and TNF-$\alpha$ and fibrogenic cytokine, TGF-$\beta$, by peripheral blood mononuclear cells (PBMC) after LPS stimulation under serum-free conditions, which lacks LBPs. Methods : PBMC were obtained by centrifugation on Ficoll Hypaque solution of peripheral venous bloods from healthy normal subjects, then stimulated in the presence of LPS (0.1 ${\mu}g/mL$ to 100 ${\mu}g/mL$ ). The activities of IL-1, IL-6, TNF, and TGF-$\beta$ were measured by bioassaies using cytokines - dependent proliferating or inhibiting cell lines. The cellular sources producing the cytokines was investigated by immunohistochemical stains and in situ hybridization. Results : PBMC started to produce IL-6, TNF-$\alpha$ and TGF-$\beta$ in 1 hr, 4 hrs and 8hrs, respectively, after LPS stimulation. The production of IL-6, TNF-$\alpha$ and TGF-$\beta$ continuously increased 96 hrs after stimulation of LPS. The amount of production was 19.8 ng/ml of IL-6 by $10^5$ PBMC, 4.1 ng/mL of TNF by $10^6$ PBMC and 34.4 pg/mL of TGF-$\beta$ by $2{\times}10^6$ PBMC. The immunoreactivity to IL-6, TNF-$\alpha$ and TGF-$\beta$ were detected on monocytes in LPS-stimulated PBMC. Some of lymphocytes showed positive immunoreactivity to TGF-$\beta$. Double immunohistochemical stain showed that IL-1$\beta$, IL-6, TNF-$\alpha$ expression was not associated with CD14 postivity on monocytes. IL-1$\beta$, IL-6, TNF-$\alpha$ and TGF-$\beta$mRNA expression were same as observed in immunoreactivity for each cytokines. Conclusion: When monocytes are stimulated with LPS under serum-free conditions, IL-6 and TNF-$\alpha$ are secreted in early stage of inflammation. In contrast, the secretion of TGF-$\beta$ arise in the late stages and that is maintained after 96 hrs. The main cells releasing IL-1$\beta$, IL-6, TNF-$\alpha$ and TGF-$\beta$ are monocytes, but also lymphocytes can secret TGF-$\beta$.

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