• Title/Summary/Keyword: LiBr

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Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde

  • Lu, Xiuhui;Li, Yongqing;Ming, Jingjing
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3690-3694
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    • 2013
  • The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

ALEX1 Regulates Proliferation and Apoptosis in Breast Cancer Cells

  • Gao, Yue;Wu, Jia-Yan;Zeng, Fan;Liu, Ge-Li;Zhang, Han-Tao;Yun, Hong;Song, Fang-Zhou
    • Asian Pacific Journal of Cancer Prevention
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    • v.16 no.8
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    • pp.3293-3299
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    • 2015
  • Background: Arm protein lost in epithelial cancers, on chromosome X (ALEX) is a novel subgroup within the armadillo (ARM) family, which has one or two ARM repeat domains as opposed to more than six-thirteen repeats in the classical Armadillo family members. Materials and Methods: In the study, we explore the biological functions of ALEX1 in breast cancer cells. Overexpression of ALEX1 and silencing of ALEX1 were performed with SK-BR3 and MCF-7 cell lines. Cell proliferation and colony formation assays, along with flow cytometry, were carried out to evaluate the roles of ALEX1. Results: ALEX1 overexpression in SK-BR3 breast cancer cells inhibited proliferation and induced apoptosis. Furthermore, depletion of ALEX1 in MCF-7 breast cancer cells increased proliferation and inhibited apoptosis. Additional analyses demonstrated that the overexpression of ALEX1 activated the intrinsic apoptosis cascades through up-regulating the expression of Bax, cytosol cytochrome c, active caspase-9 and active caspase-3 and down-regulating the levels of Bcl-2 and mitochondria cytochrome c. Simultaneouly, silencing of ALEX1 inhibited intrinsic apoptosis cascades through down-regulating the expression of Bax, cytosol cytochrome c, active caspase-9, and active caspase-3 and up-regulating the level of Bcl-2 and mitochondria cytochrome c. Conclusions: Our data suggest that ALEX1 as a crucial tumor suppressor gene has been involved in cell proliferation and apoptosis in breast cancer, which may serve as a novel candidate therapeutic target.

The α-Effect and Mechanism of Reactions of Y-Substituted Phenyl Benzenesulfonates with Hydrogen Peroxide Ion

  • Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2393-2397
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    • 2009
  • Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.

Precise Synthesis of Dendron-Like Hyperbranched Polymers and Block Copolymers by an Iterative Approach Involving Living Anionic Polymerization, Coupling Reaction, and Transformation Reaction

  • Hirao Akira;Tsunoda Yuji;Matsuo Akira;Sugiyama Kenji;Watanabe Takumi
    • Macromolecular Research
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    • v.14 no.3
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    • pp.272-286
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    • 2006
  • Dendritic hyperbranched poly(methyl methacrylate)s (PMMA)s, whose branched architectures resemble the 'dendron' part(s) of dendrimer, were synthesized by an iterative methodology consisting of two reactions in each iteration process: (a) a coupling reaction of u-functionalized, living, anionic PMMA having two tert-butyldimethylsilyloxymethylphenyl(SMP) groups with benzyl bromide(BnBr)-chain-end-functionalized PMMA, and (b) a transformation reaction of the introduced SMP groups into BnBr functionalities. These two reactions, (a) and (b), were repeated three times to afford a series of dendron-like, hyperbranched (PMMA)s up to third generation. Three dendron-like, hyperbranched (PMMA)s different in branched architecture were also synthesized by the same iterative methodology using a low molecular weight, functionalized 1,1-diphenylalkyl anion prepared from sec-BuLi and 1,1-bis(3-tert-butyldime-thylsilyloxymethylphenyl)ethylene in the reaction step (b) in each iterative process. Furthermore, structurally similar, dendron-like, hyperbranched block copolymers could be successfully synthesized by the iterative methodology using $\alpha$-functionalized, living, anionic poly(2-(perfluorobutyl) ethyl methacrylate) (PRfMA) in addition to $\alpha$-functionalized, living PMMA. Accordingly, the resulting block copolymers were comprised of both PMMA and PRfMA segments with different sequential orders. After the block copolymers were cast into films and annealed, their surface structures were characterized by angle-dependent XPS and contact angle measurements. All three samples showed significant segregation and enrichment of PRfMA segments at the surfaces.

Hydrogen ion-selective membrane electrodes based on tetrabenzylalkylenediamine (Tetrabenzylalkylenediamine을 이용한 수소이온 선택성 막전극)

  • Kim, Jae-Woo;Cho, Dong-Hoe;Jeong, Seong-Suk;Chung, Koo-Chun;Park, Myon-Yong
    • Analytical Science and Technology
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    • v.10 no.3
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    • pp.161-167
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    • 1997
  • This is on hydrogen ion-selective memebrane electrodes which were made of tetrabenzylmethylenediamine (TBMDA), tetrabenzylethylenediamine (TBEDA), tetrabenzylpropylenediamine(TBPDA) and tetrabenzylhexylenediamine(TBHDA) as neutral carriers. Their response potentials to carbon number between amino groups showed linear selectivities to hydrogen ion in the range of pH 1~pH 9, pH 2~pH 9, pH 3~pH 9 and pH 4~pH 9 and slopes were 48mV/pH, 52mV/pH, 64mV/pH, 59mV/pH respectively. The interferences effect on the cations were measured to alkali metal ions($Li^+$, $Na^+$, $K^+$), alkaline earth metal ions ($Mg^{2+}$, $Ca^{2+}$, $Sr^{2+}$, $Ba^{2+}$), transition metals ions($Cu^{2+}$, $Ni^{2+}$, $Co^{2+}$) and anions($I^-$, $Br^-$, ${NO_3}^-$, $SCN^-$), and selectivity coefficients were measured by separate-solution method. The membrane electrode made of TBMDA among the electrodes showed the best selectivity in acidic solution.

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Development and characterization of a fully functional small anti-HER2 antibody

  • Gao, Jie;Li, Bohua;Li, Huimei;Zhang, Xunmin;Zhang, Dapeng;Zhao, Lei;Wang, Chong;Fang, Chen;Qian, Weizhu;Hou, Sheng;Kou, Geng;Wei, Huafeng;Shi, Shu;Wang, Hao;Guo, Yajun
    • BMB Reports
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    • v.42 no.10
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    • pp.636-641
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    • 2009
  • The penetrating of monoclonal antibodies (mAbs) into solid tumor may be hampered by their large size. The antibody mimetics, composed of two complementarity-determining regions (CDRs) through a cognate framework region (FR), have been demonstrated to have the capacity to penetrate tumors superior to its parental intact IgG. In this study, we used CDR and FR sequences from the humanized anti-HER2 monoclonal antibody trastuzumab to design four antibody mimetics. Then these antibody mimetics were fused to human IgG Fc to generate mimetics-Fc small antibodies. One of the four mimetics-Fc antibodies binds well to HER2-overexpressing SK-BR3 cells and effectively inhibits the binding of trastuzumab. This mimetics-Fc, denoted as HMTI-Fc, was shown to be effective in mediating antibody-dependent cellular cytotoxicity and exhibit an antiproliferative effect in SK-BR3 cells. To our knowledge, the HMTI-Fc antibody shown here is the smallest fully functional antibody and may have a potential for treatment of cancer.

Hydrogeochemical Characteristics of Groundwater on Well Depth Variation in the Heunghae Area, Korea (심도 변화에 따른 흥해지역 지하수의 수리 지화학적 특성)

  • Yun Uk;Cho Byong-Wook
    • The Journal of Engineering Geology
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    • v.15 no.4 s.42
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    • pp.391-405
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    • 2005
  • Chemical and isotopic analysis for stream water, shallow groundwater, intermediate groundwater and deep groundwater was carried out to grasp hydrogeochemical characteristics of groundwater in the Heunghae area, Pohang city. Water type of stream water and shallow groundwaters is typified as Ca-Cl type, intermediate groundwater is $Na-HCO_3$, and deep groundwater is prominent in Wa-Cl type. $HCO_3^-\;and\;SiO_2$ in shallow groundwater are originated from weathering of silicate minerals, whereas those of deep groundwaters are resulted from weathering of carbonate minerals. Ca and Mg ions in both shallow and deep groundwaters are resulted from weathering of calcite and dolomite. $SO_4^{2-}$ in shallow groundwater is originated mainly from pyrite oxidation. As well depth increases, pH and TDS increase, but Eh and DO decrease. Alkali metal contents(K, Na, Li) increases as well depth increases, but alkali earth metal(Mg, Ca) and hi concentrations increase as well depth decreases. Anions, halogen elements(F, Cl, Br), and $HCO_3$ contents increase as well depth increases. The average stable isotope value of the groundwater of each depth is as follows; deep groundwater: ${\delta}^{18}O=-10.1\%o,\;{\delta}D=-65.8\%_{\circ}$, intermediate groundwater: ${\delta}^{18}O=-8.9\%_{\circ},\;{\delta}D=-59.6\%_{\circ}$, shallow groungwater : ${\delta}^{18}O=-8.0\%_{\circ},\;{\delta}D=-53.6\%_{\circ}$, surface water : ${\delta}^{18}O=-7.9\%_{\circ},\;{\delta}D=-53.3\%_{\circ}$ respectively.

Increment of Physiologically Active Compounds in Germinated Brown Rice Treated with Chitosan and its Effect on Obesity of Rat Fed a High Fat Diet (키토산을 처리한 발아현미의 기능성분 증대 및 비만에 미치는 영향)

  • Li, Hua;Cho, Jeong-Yong;Gao, Tian-Cheng;Choi, Cha-Ran;Lee, Kang-Deok;Cho, Ji-Eun;Cho, Geon-Sik;Ham, Kyung-Sik
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.37 no.8
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    • pp.985-991
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    • 2008
  • This study was to investigated the changes of physiologically active components in germinated brown rice treated with chitosan (CGBR) and its anti-obesity effect in rat fed a high fat diet. Contents of physiologically active compounds such as total phenolic compounds, total dietary fiber, $\gamma$-aminobutyric acid (GABA), and total phytic acid in CGBR were significantly higher than those of traditional germinated brown rice (GBR). Lipase inhibitory activity of CGBR was higher than those of GBR and brown rice (BR). High fat diets containing CGBR, GBR, and BR were administered to three groups of male Sprague-Dawley rats for four weeks. All groups showed no significant difference in body weight, total abdominal fat, and plasma lipid levels. However, CGBR group appeared to have lower body weight gain and total abdominal fat level than other groups fed high fat diets containing GBR and BR. Total cholesterol and LDL-cholesterol contents in plasma of CGBR group were also lower than those of other groups. Thus, new germination method of brown rice using chitosan is a useful process, which utilizes plant defense responses to elevate the production of secondary metabolites and anti-obesity effect.

Synthesis and Solution Properties of Zwitterionic Copolymer of Acrylamide with 3-[(2-Acrylamido)dimethylammonio]propanesulfonate

  • Xiao, Hui;Hu, Jing;Jin, Shuailin;Li, Rui Hai
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2616-2622
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    • 2013
  • A novel zwitterionic monomer 3-[(2-acrylamido)dimethylammonio]propanesulfonate (DMADAS) was designed and synthesized in this study. Then it was polymerized with acrylamide (AM) by free radical polymerization in 0.5 mol/L NaCl solution with ammonium persulfate ($(NH_4)_2S_2O_8$) and sodium sulfate ($NaHSO_3$) as initiator. The structure and composition of DMADAS and acrylamide-3-[(2-acrylamido)-dimethylammonio]propanesulfonate copolymer (P-AM-DMADAS) were characterized by FT-IR spectroscopy, $^1H$ NMR and elemental analyses. Isoelectric point (IEP) of P-AM-DMADAS was tested by nanoparticle size and potential analyzer. Solution properties of copolymer were studied by reduced viscosity. Antipolyelectrolyte behavior was observed and was found to be enhanced with increasing DMADAS content in copolymer. The results showed that the viscosity of P-AM-DMADAS is 5.472 dl/g in pure water. Electrolyte was added, which weakened the mutual attraction between sulfonic acid group and quaternary ammonium group. The conformation became loose, which led to the increase of reduced viscosity. The ability of monovalent and divalent cation influencing the viscosity of zwitterionic copolymer obeyed the following sequence: $Li^+$ < $Na^+$ < $K^+$, $Mg^{2+}$ < $Ca^{2+}$ < $Ba^{2+}$, and that of anion is in the order: $Cl^-$ < $Br^-$ < $I^-$, $CO{_3}^{2-}$ > $SO{_3}^{2-}{\approx}SO{_4}^{2-}$.

Selective Solvation and Reasonable Solvation Number of Some Univalent Ions in Water-Ethanol Systems (물-에탄올 混合溶媒에서 몇가지 1가 이온들의 選擇的 溶媒和와 妥當한 溶媒和數)

  • Kim, Hag-Sung
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.589-597
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    • 1995
  • In water-ethanol systems, the limiting equivalent conductances of electrolytes were obtained using conductometric method. Using TATB method, the limiting equivalent ionic conductances of Li+, Na+, K+, Cl-, and Br- ions were also obtained. The effective radii of corresponding ions were determined using Nightingale method. From the volume of the solvation shell, the four solvation numbers were suggested. The reasonable solvation numbers (hH2O+hO) were estimated by comparing the values obtained by from the various suggested methods. The isosolvation point of ion in water-ethanol estimated was found to be larger than that of in water-methanol. This result agree with ET (solvent polarity) values of solvents. From the reasonable solvation numbers of ions in water-ethanol, the selective solvents of corresponding ions in water-ethanol were obtained.

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