• 제목/요약/키워드: Solution NMR

검색결과 565건 처리시간 0.026초

Novel Pseudoceramides And Their Synthesis Using Alkyl Ketene Dimer

  • Park, Byeong-Deog;Lee, Ki-Mu;Park, Ik-Ju;Song, Young-Jin;Lee, Jung-Suk;Lee, Myung-Jin
    • 대한화장품학회지
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    • 제23권3호
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    • pp.92-96
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    • 1997
  • Nowadays, ceramides have been found to be an important component in the outermost layer of the skin - the stratum corneum. It is undersrood that ceramides play an important role in structure and maintenance of the interellular lipid lamella structure in the SC layer. Thus, many efforts have been made by the cosmetics and pharmaceutical industries to get human skin-identical ceramides or pseudoceramides which show similar performance with natural ceramides. The purpose of our study was to systhesize new pseudoceramides via an effective and economical systhetic pathway and to show their performance of skin restoratio. Four kinds of the new pseudoceramides were synthesized by the reaction of alcoholic amine and alkyl ketene dimer. First of all, PC-4 and PC-5 were synthesized by the reaction of 3-amino-1,2-propanidiol and serinol with alkyl ketene dimer respectively. After that, PC-4R and PC-5R were produced by changign kitone group at $\beta$-position to amide bond of above synthesized PC-4 and PC-5 into hydroxyl group using NaBH4 respectively. Their expected structures were conformed by the NMR, IR spectra, and elemental analysis. A study to show the restoration effectiveness was performed in which human skin was pretreated with high concentration of SDS surfactant solution. Using 0.5% solution of above synthesized pseudoceramides, there was the significantly faster restoration of the damaged than that of placebe itself treatment.

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몰리브덴(Ⅲ) 과 바나듐(Ⅲ) 호모 및 헤테로 이핵 착물의 합성과 특성 (제 4 보) (Synthesis and Characterization of Homo-, Hetero-Dinuclear Mo(Ⅲ) and V(Ⅲ) Complexes (Ⅳ))

  • 오상오;유은영
    • 대한화학회지
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    • 제38권11호
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    • pp.808-818
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    • 1994
  • $MCl_z$(M = Mo; z = 5, M = V; z = 3)과 N,P 주개 리간드를 acetonitrile 용매에서 반응시켜 중성착물 [$MCl_3L_2$(MeCN)] (M = Mo, V: L = $PPh_3$, 1/2 phda)을 합성하였다. Acetone 용액에서 이들 중성 화합물과 $AgClO_4$를 반응시켜 [$MCl_3-_nL_2(MeCN)(S)_n$]$(ClO_4)_n$ (n = 1, 2 : s = solvent)의 양이온 화합물을 얻었다. 2가의 양이온 화합물과 중성 화합물을 반응시켜 염소가 다리 연결된 이핵 화합물 $[(MeCN)(L)_2ClM({\mu}-Cl)_2M'Cl(L)_2(MeCN)](ClO_4)_2$ 및 1가의 양이온 화합물과 pyzidine을 2:1 화학양론으로 반응시켜 pyzidine이 다리 결합된 이핵 화합물 $[(MeCN)(L)_2Cl_2M({\mu}-pyz)M'Cl_2(L)_2(MeCN)](ClO_4)_2$형의 호모(M = M'), 헤테로(M ${\neq}$ M') 화합물을 합성하였다. 합성한 착물들은 원소분석과 적외선, $^1H$, $^{13}C$ 핵자기 공명 및 전자 흡수스펙트럼 등을 이용하여 그 특성을 조사하였다.

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Solution Structure of an Active Mini-Proinsulin, M2PI: Inter-chain Flexibility is Crucial for Insulin Activity

  • Cho, Yoon-Sang;Chang, Seung-Gu;Choi, Ki-Doo;Shin, Hang-Cheol;Ahn, Byung-Yoon;Kim, Key-Sun
    • BMB Reports
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    • 제33권2호
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    • pp.120-125
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    • 2000
  • M2PI is an active single chain mini-proinsulin with a 9-residue linker containing the turn-forming sequence 'YPGDV' between the B- and A-chains, but which retains about 50% of native insulin receptor binding activity. The refolding efficiency of M2PI is higher than proinsulin by 20-40% at alkaline pH, and native insulin is generated by the enzymatic conversion of M2PI. The solution structure of M2PI was determined by NMR spectroscopy. The global structure of M2PI is similar to that of native insulin, but the flexible linker between the B- and A-chains perturbed the N-terminal A-chain and C-terminal B-chain. The helix in the N-terminal A-chain is partly perturbed and the ${\beta}$-turn in the B-chain is disrupted in M2PI. However, the linker between the two chains was completely disordered indicating that the designed turn was not formed under the experimental conditions (20% acetic acid). Considering the fact that an insulin analogue, directly cross-linked between the C-terminus of the B-chain and the N-terminus of the A-chain, has negligible binding activity, a flexible linker between the two chains is sufficient to keep binding activity of M2PI, but the perturbed secondary structures are detrimental to receptor binding.

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Oligo(oxy ethylene) pendant를 갖는 PBO 전구체의 합성 및 특성 (Synthesis and Properties of Polybenzoxazole Precursors having Oligo(oxy ethylene) pendant)

  • 이응재;윤두수;방문수;최재곤
    • 한국산학기술학회논문지
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    • 제14권5호
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    • pp.2550-2558
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    • 2013
  • 주사슬에 oligo(oxy ethylene) 팬던트를 갖는 poly(o-hydroxyamides)(PHAs) 공중합체를 저온에서 용액 중축합 반응에 의해서 합성하였다. 이들 공중합 전구체들의 특성은 1H-NMR, FT-IR, DSC, TGA, UTM 그리고 LOI 등을 이용하여 조사하였다. $35^{\circ}C$의 DMAc 또는 DMAc/LiCl 용액하에서 측정된 PHAs의 고유점성도는 0.74~1.42 dL/g의 범위를 보였다. 전구체들의 용해도는 oligo(oxy ethylene) 단위의 증가와 함께 증가하였으나, polybenzexazoles(PBOs)는 다양한 용매에도 거의 용해되지 않았다. 공중합 전구체들의 분해온도는 질소분위기하에서 $408{\sim}664^{\circ}C$의 범위를 보였고, $900^{\circ}C$에서 char 수득률은 13~59%의 값을 보였다. 공중합 전구체들의 기계적 성질과 난연특성은 oligo(oxy ethylene) 단위가 증가함에 따라 감소하였다.

N'-phenyl-N-(2-chloroethyl)-N-nitrosourea 유사체의 전기화학적 거동 및 N-aminourea의 합성 (Electrochemical Behaviors of N'-phenyl-N-(2-chloroethyl)-N-nitrosourea Analogous and Synthesis of N-aminourea)

  • 원미숙;김정균;심윤보
    • 대한화학회지
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    • 제35권6호
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    • pp.707-712
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    • 1991
  • 수은 pool 전해조를 사용하여 (5:3) EtOH/4N-HCl 용액계에서 선택적인 -N-N=O기의 전기화학적 환원에 의해 N'-phenyl-N-(2-chloroethyl)-N-nitrosourea로부터 N'-phenyl-N-(2-chloroethyl)-N-aminourea를 합성하였다. 전기화학적 환원에 앞서 반응의 최적조건을 검토하기 위하여 몇 가지 N'-aryl-N-(2-chloroethyl)-N-nitrosourea 유사체에 대하여 pH변화에 따른 환원전위를 순환전압전류법으로 조사한 결과 pH에 따라 $E_p$값이 "-"쪽으로 이동하였으며 aryl기의 치환기 효과는 -N-N=O기의 환원 전위에 크게 영향을 미치지 않는 것으로 나타났다. 용액계의 pH에 따른 반응성을 조사한 결과 강산성 용액(pH<1)에서 반응이 가장 잘 진행되며 -0.7 V vs. Ag/AgCl/4 N-HCl에서 N-N=O기의 선택적인 4전자 환원반응에 의해 N-N$H_2$가 생성됨을 확인하였다.

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Non-monotonic Size Dependence of Electron Mobility in Indium Oxide Nanocrystals Thin Film Transistor

  • Pham, Hien Thu;Jeong, Hyun-Dam
    • Bulletin of the Korean Chemical Society
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    • 제35권8호
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    • pp.2505-2511
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    • 2014
  • Indium oxide nanocrystals ($In_2O_3$ NCs) with sizes of 5.5 nm-10 nm were synthesized by hot injection of the mixture precursors, indium acetate and oleic acid, into alcohol solution (1-octadecanol and 1-octadecence mixture). Field emission transmission electron microscopy (FE-TEM), High resolution X-Ray diffraction (X-ray), Nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopy (FT-IR) were employed to investigate the size, surface molecular structure, and crystallinity of the synthesized $In_2O_3$ NCs. When covered by oleic acid as a capping group, the $In_2O_3$ NCs had a high crystallinity with a cubic structure, demonstrating a narrow size distribution. A high mobility of $2.51cm^2/V{\cdot}s$ and an on/off current ratio of about $1.0{\times}10^3$ were observed with an $In_2O_3$ NCs thin film transistor (TFT) device, where the channel layer of $In_2O_3$ NCs thin films were formed by a solution process of spin coating, cured at a relatively low temperature, $350^{\circ}C$. A size-dependent, non-monotonic trend on electron mobility was distinctly observed: the electron mobility increased from $0.43cm^2/V{\cdot}s$ for NCs with a 5.5 nm diameter to $2.51cm^2/V{\cdot}s$ for NCs with a diameter of 7.1 nm, and then decreased for NCs larger than 7.1 nm. This phenomenon is clearly explained by the combination of a smaller number of hops, a decrease in charging energy, and a decrease in electronic coupling with the increasing NC size, where the crossover diameter is estimated to be 7.1 nm. The decrease in electronic coupling proved to be the decisive factor giving rise to the decrease in the mobility associated with increasing size in the larger NCs above the crossover diameter.

In situ Gel Forming Stereocomplex Composed of Four-Arm PEG-PDLA and PEG-PLLA Block Copolymers

  • Jun, Yeo-Jin;Park, Kyung-Min;Joung, Yoon-Ki;Park, Ki-Dong;Lee, Seung-Jin
    • Macromolecular Research
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    • 제16권8호
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    • pp.704-710
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    • 2008
  • Injectable hydrogels are quite promising materials due to their potential to minimize invasive implantation and this provides versatile fitness irrespective of the damaged regions and facilitates the incorporation of bioactive agents or cells. In situ gel formation through stereocomplex formation is a promising candidate for injectable hydrogels. In this paper, a new series of enantiomeric, four-arm, PEG-PLA block copolymers and their stereocomplexed hydrogels were prepared by bulk ring-opening polymerization of D-lactide and L-lactide, respectively, with stannous octoate as a catalyst. The prepared polymers were characterized by $^1H$ nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FT IR) spectroscopy, gel permeation chromatography (GPC) and thermal gravitational analysis (TGA), confirming the tailored structure and chain lengths. The swelling and degradation behavior of the hydrogels formed from a selected copolymer series were observed in different concentrations. The degradation rate decreased with increasing polymer content in the solution. The rheological behavior indicated that the prepared hydrogel underwent in situ gelation and had favorable mechanical strength. In addition, its feasibility as an injectable scaffold was evaluated using a media dependence test for cell culture. A Tris solution was more favorable for in situ gel formation than PBS and DMEM solutions were. These results demonstrated the in situ formation of hydrogel through the construction of a stereocomplex with enantiomeric, 4-arm, PEG-PLA copolymers. Overall, enantiomeric, 4-arm, PEG-PLA copolymers are a new species of stereocomplexed hydrogels that are suitable for further research into injectable hydrogels.

Structural and Functional Characterization of CRAMP-18 Derived from a Cathelicidin-Related Antimicrobial Peptide CRAMP

  • Park, Kyong-Soo;Shin, Song-Yub;Hahm, Kyung-Soo;Kim, Yang-Mee
    • Bulletin of the Korean Chemical Society
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    • 제24권10호
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    • pp.1478-1484
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    • 2003
  • CRAMP was identified from a cDNA clone derived from a mouse femoral marrow cells as a member of cathelicidin-derived antimicrobial peptide. Tertiary structure of CRAMP in TFE/$H_2O$ (1 : 1, v/v) solution has been determined by NMR spectroscopy previously and consists of two amphipathic $\alpha-helices$ from Leu4 to Lys10 and from Gly16 to Leu33. These two helices are connected by a flexible region from Gly11 to Gly16. Analysis of series of fragments composed of various portion of CRAMP revealed that an 18-residue fragment with the sequence from Gly16 to Leu33 (CRAMP-18) was found to retain antibacterial activity without cytotoxicity. The effects of two Phe residues at positions 14 and 15 of CRAMP-18 on structure, antibacterial activity, and interaction with lipid membranes were investigated by $Phe^{14,15}$ ${\rightarrow}$ Ala substitution (CRAMP-18-A) in the present study. Substitution of Phe with Ala in CRAMP-18 caused a significant reduction on antibacterial and membrane-disrupting activities. Tertiary structures of CRAMP-18 in 50% TFE/$H_2O$ (1 : 1, v : v) solution shows amphipathic ${\alpha}$-helix, from $Glu^2{\;}to{\;}Leu^{18}$, while CRAMP-18-A has relatively short amphipathic ${\alpha}$-helix from $Leu^4{\;}to{\;}Ala^{15}$. These results suggest that the hydrophobic property of $Phe^{14}{\;}and{\;}Phe^15$ in CRAMP-18 is essential for its antibacterial activity, ${\alpha}$-helical structure, and interactions with phospholipid membranes.

Conductance Study on the Characteristics of Solution Containing Crown Ethers and Univalent Cation Perchlorates

  • Lee, Shim-Sung;Park, Sung-Oh;Jung, Jong-Hwa;Lee, Bu-Yong;Kim, Si-Joong
    • Bulletin of the Korean Chemical Society
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    • 제11권4호
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    • pp.276-281
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    • 1990
  • The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

Backbone 1H, 15N, and 13C Resonance Assignments and Secondary Structure of a Novel Protein OGL-20PT-358 from Hyperthermophile Thermococcus thioreducens sp. nov.

  • Wilson, Randall C.;Hughes, Ronny C.;Curto, Ernest V.;Ng, Joseph D.;Twigg, Pamela D.
    • Molecules and Cells
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    • 제24권3호
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    • pp.437-440
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    • 2007
  • $OGL-20P^T$-358 is a novel 66 amino acid residue protein from the hyperthermophile Thermococcus thioreducens sp. nov., strain $OGL-20P^T$, which was collected from the wall of the hydrothermal black smoker in the Rainbow Vent along the mid-Atlantic ridge. This protein, which has no detectable sequence homology with proteins or domains of known function, has a calculated pI of 4.76 and a molecular mass of 8.2 kDa. We report here the backbone $^1H$, $^{15}N$, and $^{13}C$ resonance assignments of $OGL-20P^T$-358. Assignments are 97.5% (316/324) complete. Chemical shift index was used to determine the secondary structure of the protein, which appears to consist of primarily ${\alpha}$-helical regions. This work is the foundation for future studies to determine the three-dimensional solution structure of the protein.