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Ring-Opening Polymerization of $\varepsilon$-Caprolactone and Cyclohexene Oxide Initiated by Aluminum $\beta$-Ketoamino Complexes: Steric and Electronic Effect of 3-Position Substituents of the Ligands

  • Liu, Binyuan;Li, Haiqing;Ha, Chang-Sik;Kim, Il;Yan, Weidong
    • Macromolecular Research
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    • 제16권5호
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    • pp.441-445
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    • 2008
  • A series of aluminum complexes supported by $\beta$-ketoamino, ligand-bearing, 3-position substituents $LAlEt_2$ ($L=CH_3C(O)C(Cl)=C(CH_3)NAr\;(L_1)$, $L=CH_3C(O)C(H)=C(CH_3)NAr\;(L_2)$, $L=CH_3C(O)C(Ph)=C(CH_3)NAr\;(L_3)$, and $L=CH_3C(O)C(Me)=C(CH_3)NAr\;(L_4)$, $Ar=2,6-^iPr_2C6H_3$) were synthesized in situ and employed in the ring-opening polymerization (ROP) of $\varepsilon$-caprolactone ($\varepsilon$-CL) and cyclohexene oxide (CHO). The 3-position substituents on the $\beta$-ketoamino ligand backbone of the aluminum complexes influenced the catalyst activity remarkably for both ROP of $\varepsilon$-CL and CHO. Aluminum $\beta$-ketoamino complexes displayed different catalytic behavior in ROP of $\varepsilon$-CL and CHO. The order of the catalytic activity of $LAlEt_2$ was $L_1AlEt_2$>$L_2AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$ for ROP of $\varepsilon$-CL, being opposite to the electron-donating ability of the 3-position substituents on the $\beta$-ketoamino ligand, while the order of the catalytic activity for ROP of CHO was $L_1AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$>$L_2AlEt_2$. The effects of reaction temperature and time on the ROP were also investigated for both $\varepsilon$-CL and CHO.

Palladium(II) Schiff Base Complexes Derived from Allylamine and Vinylaniline

  • Uh, Yoon-Seo;Zhang, Hai-Wen;Vogels, Christopher M.;Decken, Andreae;Westcott, Stephen A.
    • Bulletin of the Korean Chemical Society
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    • 제25권7호
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    • pp.986-990
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    • 2004
  • Condensation of salicylaldehyde $(2-HOC_6H_4C(O)H)$ with allylamine afforded the unsaturated salicylaldimine, $2-HOC_6H_4C(H)=NCH_2CH=CH_2$. Similar reactivity was observed with substituted salicylaldehydes. Further reaction of these Schiff bases with palladium acetate or $Na_2PdCl_4$ afforded complexes of the type $PdL_2$, where L = deprotonated Schiff base. The molecular structure of the parent salicylaldimine palladium complex $[trans-(2-OC_6H_4C(H)=NCH_2CH=CH_2)_2Pd]$ (1) was characterized by an X-ray diffraction study. Crystals of 1 were monoclinic, space group $P2_1/n,\;a\;=\;14.0005(9)\;{\AA},\;b\;=7.2964(5)\;{\AA},\;c\;=\;17.5103(12)\;{\AA},\;{\beta}\;=\;100.189(1)^{\circ}$, Z = 4. Analogous chemistry with 4-vinylaniline also gave novel palladium complexes containing a pendant styryl group. Crystals of $[trans-(2-HOC_6H_4C(H)=N-4-C_6H_4CH=CH_2)_2Pd]$ (4) were monoclinic, space group $P2_1/c$, a = 13.7710(14) ${\AA}$, b = 11.0348(11) ${\AA}$, c = 7.8192(8) ${\AA}$, ${\beta}\;=\;98.817(2)^{\circ}$, Z = 2.

발기부전 처방에 사용되는 쇄양(鎖陽)이 음경해면체 이완에 미치는 영향 (The Relaxation Effects of Cynomorii herba in Isolated Corpus Cavernosum Tissues)

  • 신선미;박선영
    • 대한한방내과학회지
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    • 제37권4호
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    • pp.591-600
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    • 2016
  • Objective: This study aimed to examine the relaxation effects and underlying mechanisms of Cynomorii herba (CH) extract in isolated rabbit corpus cavernous tissues.Methods: We experimented with CH extract (0.01-3.0 mg/mL). Nω-nitro-L-arginine (L-NNA) was experimented before the CH extract to contracted strips induced by phenylephrine (PE, 1 μM)and compared with nonexperimented. In addition, we experimented with calcium chloride (Ca2+, 1 mM) after pretreatment of the CH extract in Ca2+-free Krebs-Ringer solution to contracted strips induced by PE. The cell viability and nitric oxide (NO) concentration of human umbilical vein endothelial cells (HUVECs) were measured by an methylthiazol-2-yl-2, 5-diphenyl tetrazoliumbromide (MTT) assay and Griess reagent system. The ratio of smooth muscles to collagen fibers, in addition to eNOS- and PDE-5-positive reactions, was examined by histochemical and immunohistochemical staining.Results: The CH extract significantly induced the relaxation of the cavernous strips, and the pretreatment with L-NNA inhibited CH extract-induced relaxation. The L-NNA pretreatment reduced the increased contraction induced by the addition of Ca2+in Ca2+-free solution. Furthermore, the NO concentration of the HUVECs increased. When the CH extract was applied to the corpus cavernosum of the penis (CCP) of Sprague Dawley rats, the ratio of smooth muscles to collagen fibers by PE and the formation of eNOS around the helicine artery increased. However, the CH extract treatment decreased PDE-5 positive reactions.Conclusions: These results show that the relaxation effects induced by the CH extract are associated with the suppression of the influx of extracellular Ca2+ via the production of NO and eNOS and inhibition of PDE-5.

평면 레이저 유도 형광법(PLIF)을 이용한 $CH_4/O_2N_2$ 예혼합화염의 NO 농도 분포 가시화에 관한 연구 (A Study on the Visualization of NO Concentration Distributions in $CH_4/O_2N_2$ Premixed Flames by PLIF)

  • 박경석;이세환
    • 한국분무공학회지
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    • 제6권3호
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    • pp.1-7
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    • 2001
  • In this study, quantitative measurement of nitric oxide concentration distributions visualization were investigated in the laminar $CH_4/O_2N_2$ nixed flame by Planar laser-induced fluorescence(PLIF). The NO A-X (0,0) vibrational band around 226nm was excited using a XeCl excimer-pumped dye laser. Selecting an appropriate NO transition minimizes interference from Rayleigh scattering and $O_2$ fluorescence. The measurements were taken in $CH_4/O_2N_2$ premixed flame with equivalence ratios varying from $1.0{\sim}1.6$, and a fixed flow rate of 3slpm. NO was found to produce primarily between an inner premixed and an outer nonpremixed flame front, and total NO concentration is raised when equivalence ratios increase. These results suggest that prompt NO is likely to contribute to MO formation in $CH_4/O_2N_2$ premixed flame. Furthermore, this trend was well matched with previous works.

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Intracluster Ion/Molecule Reactions within 1,1-Difluoroethylene Homocluster

  • 이선영;최창주;정경훈
    • Bulletin of the Korean Chemical Society
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    • 제18권3호
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    • pp.296-300
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    • 1997
  • The intracluster ion/molecule reactions within 1,1-difluoroethene homocluster have been studied by electron-impact quadrupole mass spectrometry. When CH2CF2 seeded in helium is expanded and ionized by electron impact, two different types of ion/molecule association (polymerization) reaction products, i.e., (CH2CF2)n+ (n≥l) and (CF2CH2)qX+ (X=fragment species, q≤n), are formed. The higher association products, (CH2CF2)n+ (n=3, 4), have shown stronger intensities over the lower association product, (CH2CF2)2+, in the low electron impact energy region ( < 39 eV). These stronger intensities are interpreted in terms of the stabilization of these ions due to the ring formations over the dimer ion in this energy region. The evidence of ring formation mechanism is on the basis of the intensity distribution of fragments at various electron impact energy. In another typical branched-chain growth reaction of these compounds, the F-shift reaction path is found to be more favorable energetically than the H-shift via the fragment patterns of clusters and semi-empirical calculation.

증기압에 미치는 동위원소 효과 (Isotope Effects on Vapor Pressure)

  • 오영기;전무식
    • 대한화학회지
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    • 제21권2호
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    • pp.75-82
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    • 1977
  • 순수한 액체의 증가압에 미치는 동위원소 효과를 연구하였고, 증기압 비를 계산하였다. Significant Structure Theory of Liquid를 사용한 계산결과에 의하면, $C_2H_4/C_2H_2D_2$(trans)계 에서는 분자량과 관성능률에 의한 효과가 현저하고, $C_2H_2D_2(trans)/C_2H_2D_2(cis)$계에서는 분자 회전이 자유롭지 못한 데서 오는 영점에너지 효과가 현저했다. 그리고, $CH_3OH/CH_3OD$계에서는 분자간 인력이 동위원소에 따라 다르기 때문임이 밝혀졌다. $CH_4/CD_4,\;SiH_4/SiD_4,\;GeH_4/GeD_4$ 동위원소계에서는 분자량에 의한 효과가 $CH_4/CD_4 >SiH_4/SiD_4 >GeH_4/GeD_4$의 순서로 감소함을 알 수 있었다.

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1-브로모실라트란의 $SnBr_2$ 에 대한 산화성 첨가반응 연구 (Studies on the Oxidative Addition Reactions of 1-Bromosilatranes to $SnBr_2$)

  • 김명운;어동선;신호철;김진권;도영규
    • 대한화학회지
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    • 제38권3호
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    • pp.241-245
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    • 1994
  • 산화성 첨가반응을 이용하여 실라트란(분자내 Si-N고리횡단 상호작용을 갖는 5-배위의 규소화합물)의 규소원자와 주족원소간에 Si-M 결합작용이 있는 새로운 이종다핵 화합물을 합성하려고 시도하였다. 1-브로모실라트란(1a)과 $SnBr_2를 반응시켜 노란색(2a)과 흰색(2b)의 고체 혼합물을 얻었고 용해도 차에 의해 각각을 분리하여 ^1H-NMR, ^{29}Si-NMR, ^{119}Sn-NMR, Mass스펙트럼으로 규명한 결과 노란색 화합물만이 Si-Sn결합을 갖는 것으로 판명되었다. SnBr_2를 1-브로모-3,7,10-트리메틸실라트란(1b)과도 반응시켜 Si-Sn 결합을 갖는 화합물, N[CH_2CH(CH_3)O]_3SiSnBr_3(CH_3OH)_2(3)$을 분리하여 여러가지 방법으로 확인하였다.

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Cycloplatinated Complexes of Thiosemicarbazones. Synthesis and Crystal Structure of [$Ph_2PC_6H_4CHNNC(S)NHCH_3PtCl$]

  • 유동원;강상욱;고재정;최문근
    • Bulletin of the Korean Chemical Society
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    • 제18권3호
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    • pp.305-310
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    • 1997
  • The synthesis and characterization of the platinum heterocyclic carboxaldehyde thiosemicarbazone complexes [NC5H4CRNNC(S)NHR'PtCl] (R=H, R'=CH3(1); R=CH3, R'=CH3(2); R=CH3, R=H(3)) and diphenylphosphinophenyl carboxaldehyde thiosemicarbazone complexes [Ph2PC6H4CHNNC(S)NHRPtCl] (R=CH3(5); R=iC3H7(6); R=Ph(7)) are described. Compounds 1-3 were prepared by reaction of Pt(SEt2)2Cl2 with 2-acetylpyridine-4-alkylthiosemicarbazone in the presence of NEt3. Compounds 5-7 were prepared using Pt(SEt2)2Cl2 in toluene with diphenylphosphinophenyl carboxaldehyde alkylthiosemicarbazone. The compounds have been characterized by microanalysis, NMR (1H, 13C, 31P) spectroscopy, and single-crystal X-ray diffraction. X-ray single crystal diffraction analysis reveals that compound 5 is a mononuclear platinum compound with P,N,S-coordination mode.

Effect of Cassava Hay and Rice Bran Oil Supplementation on Rumen Fermentation, Milk Yield and Milk Composition in Lactating Dairy Cows

  • Lunsin, R.;Wanapat, Metha;Rowlinson, P.
    • Asian-Australasian Journal of Animal Sciences
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    • 제25권10호
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    • pp.1364-1373
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    • 2012
  • Four crossbred (75% Holstein Friesian) lactating dairy cows, with an average live weight of $418{\pm}5$ kg and $36{\pm}10$ d in milk were randomly assigned according to a $2{\times}2$ factorial arrangement in a $4{\times}4$ Latin square design to evaluate the effects of cassava hay (CH) and rice bran oil (RBO) on feed intake, nutrient digestibility, ruminal fermentation, milk yield, and milk composition. Factor A was non-supplementation or supplementation with CH in the concentrate. Factor B was supplementation with RBO at 0% or 4% in the concentrate mixture. The four dietary treatments were (T1) control (Concentrate with non-CH plus 0% RBO; C), (T2) Concentrate with CH plus 0% RBO (CH), (T3) Concentrate with non-CH plus 4% RBO (RBO), and (T4) Concentrate with CH plus 4% RBO (CHRBO). The cows were offered concentrate, at a ratio of concentrate to milk production of 1:2, and urea-lime treated rice straw was fed ad libitum. Urea-lime treated rice straw involved 2.5 g urea and 2.5 g $Ca(OH)_2$ (purchased as hydrated lime) in 100 ml water, the relevant volume of solution was sprayed onto a 100 g air-dry (91% DM) straw, and then covering the stack with a plastic sheet for a minimum of 10 d before feeding directly to animals. The CH based concentrate resulted in significantly higher roughage intake and total DM intake expressed as a percentage of BW (p<0.05). Ruminal pH, $NH_3$-N, BUN and total VFA did not differ among treatments, while RBO supplementation increased propionate, but decreased acetate concentration (p<0.05). Furthermore, the population of total ruminal bacteria was significantly lower on the RBO diet (p<0.05). In contrast, the total ruminal bacteria and cellulolytic bacteria on the CH diet were higher than on the other treatments. Supplementation with CH increased (p<0.05) F. succinogens and R. flavefaciens populations, whereas the populations of B. fibrisolvens and M. elsdenii were increased on the RBO diet. In addition, supplementation with CH and RBO had no effect on milk production and composition in dairy cows, while fatty acid composition of milk was influenced by RBO supplementation, and resulted in significantly lower (p<0.05) concentrations of both short-chain and medium-chain FA, and increased (p<0.05) the proportion of long-chain FA in milk fat, as well as significantly increased cis-9, trans-11 CLA and total CLA. In conclusion, RBO or CH exhibited specific effects on DMI, rumen fermentation, microbial population, milk yield and composition in lactating dairy cows, which were not interactions between CH and RBO in the diets. Feeding lactating dairy cows with RBO could improve fatty acid in milk fat by increasing cis-9, trans-11 CLA.