• Title/Summary/Keyword: 고체 NMR

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Study of the Molecular Reorientation in Ammonium Sulfate by Neutron Scattering

  • Kim, Huhn-Jun
    • Nuclear Engineering and Technology
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    • v.4 no.4
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    • pp.306-321
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    • 1972
  • Molecular reorientation in (NH$_4$)$_2$SO$_4$, has been studied by cold neutron scattering. For T=300$^{\circ}$K data, the isolated quasielastic spectra and form-factors at various scattering angles are compared with four reorientational models based on SKOLD theory. Front these, it is concluded that the NH$_4$ions are performing either 3-fold four axes or 2-fold three axes reorientation with $\tau$$_{c}$=2.0$\times$10$^{-11}$ sec. The temperature dependence of f. is studied over 100$^{\circ}$K-413$^{\circ}$K and for the high-temperature phase, the widths of composite spectra are compared with the results from NMR relaxation measurements. All the results have shown that the neutron scattering method is capable of giving detalis of the reorientational modes in solids and therefore some discussions are given on the application of this method. A study of the form-factor is applied for NH$_4$I (Phase I) by comparing the measurement with the calculation based on free rotation approximation and proposed a reorientation model of NH$_4$ ions in the octahedral potential cage with $\tau$$_{c}$$\leq$10$^{-12}$ sec. Also a brief theoretical prediction for the effect of reorientational motions on the inelastic spectrum is discussed.sed.

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Preparation and Properties of Water-based Adhesive Using Gemini Type Nonionic Reactive Surfactants (제미니형 비이온 반응성 계면활성제를 이용한 수성접착제의 제조 및 특성)

  • Shin, Hye-Lin;Jeong, Noh-Hee
    • Applied Chemistry for Engineering
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    • v.30 no.5
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    • pp.597-605
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    • 2019
  • In order to improve the adhesion of water-based adhesive, gemini type nonionic reactive surfactants were synthesized and applied to water-based adhesives. The surfactants were synthesized by using maleic acid and polyoxyethylene cetyl ether having different length of ethylene oxide and confirmed by FT-IR and $^1H-NMR$. Their appearance was light yellow wax. The cloud point of the compound was more than $78^{\circ}C$. The measured critical micelle concentration (c.m.c) was $1.0{\times}10^{-4}{\sim}7.0{\times}10^{-4}mol/L$ and surface tension at c.m.c was 25.9~32.0 mN/m. As the number of ethylene oxide increased, the emulsifying power was improved. The foaming height of each compound by Ross-Miles method was 1.4~4.5 cm. The synthesized surfactants was then used as an emulsifier in emulsion polymerization of water-based adhesives and its physical properties were evaluated. The solid contents of prepared adhesives was 59%. The average particle size and initial tackiness of the prepared adhesives were 164~297 nm and ball no. of 20~32, respectively. The peel strength was $1.8{\sim}2.1kg_f/mm$. The retention rate of adhesives viscosity was evaluated to 99% during 30 days. Therefore, synthesized gemini type nonionic reactive surfactants are expected to be applied as an emulsifier for the high adhesive force.

Synthesis of AlPO4-type Mesoporous Materials Using Alum Sludge (Alum 슬러지를 이용한 AlPO4-계 다공성 물질의 합성)

  • Kang, Kwang Cheol;Kim, Young Ho;Kim, Jin-man;Lee, Choul Ho;Rhee, Seog Woo
    • Applied Chemistry for Engineering
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    • v.22 no.2
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    • pp.173-177
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    • 2011
  • In this study, the formation of $AlPO_4$-type porous materials from alum sludge was investigated. The materials were synthesized by the reaction of aluminum hydroxide and phosphoric acid with an organic template. Cationic surfactant, natural humic acid, and amino acids were used for the organic template. The residual organic templates were removed by calcination at $600^{\circ}C$ in the air. Powder X-ray diffraction patterns showed the charicteristic patterns of the $AlPO_4$-type porous materials. The morphology of the material was examined using a scanning electron microscopy. The coordination environment of $Al^{3+}$ ion was investigated by $^{27}Al$ MAS NMR technique. Both tetrahedrally and octahedrally coordinated$Al^{3+}$ ions were found in the as-synthesized samples while all $Al^{3+}$ ions were tetrahedrally coordinated in the calcined products. The development of mesopore in the solid material was confirmed by the measurement of BET specific surface area. Finally, they were used for removal of toxic formaldehyde from the air and the formaldehyde molecules were adsorbed on the surface of pores. In conclusion, $AlPO_4$-type porous materials from alum sludge might be applicable in the removal of toxic volatile organic compounds from the air.

The Effect of Structure and Acidity of Fluorinated HZSM-5 on Ethylene Aromatization (불소화 HZSM-5의 구조 및 산도가 에틸렌 방향족화에 미치는 영향)

  • Kyeong Nan, Kim;Seok Chang, Kang;Geunjae, Kwak
    • Applied Chemistry for Engineering
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    • v.34 no.1
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    • pp.15-22
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    • 2023
  • Recent studies have actively investigated ways to improve the economic feasibility and efficiency of the Fischer-Tropsch process by increasing the yields of the monocyclic aromatic compounds (BTEX). In this study, ethylene was selected as a model of F-T-derived hydrocarbons, and the ethylene-to-aromatics (ETA) reaction was investigated according to changes in acid characteristics, mesopores, and crystallinity of HZSM-5 (HZ5). Fluorinated HZ5 was prepared by calcination followed by impregnation of an aqueous NH4F solution having different molar concentrations in HZ5, and the structural and chemical properties of F/HZ5 were investigated through Brunauer-Emmett-Teller (BET), solid-state nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), NH3-temperature-programmed desorption (TPD), and pyridine-IR spectroscopy. The ETA reactions were performed at 673 K under 0.1 MPa, and fluorinating HZ5 by an aqueous NH4F solution of 0.17 M improved ethylene conversion, BTEX selectivity, and catalytic stability due to acidity, mesopore fraction, and crystallinity.

Differences in Structural Characteristics and Eu(III) Complexation for Molecular Size Fractionated Humic Acid (분자량별 분류에 따른 휴믹산의 구조적 특성 및 Eu(III)과의 착물 반응 특성 비교에 대한 연구)

  • Shin, Hyun-Sang;Rhee, Dong-Seok;Kang, Kihoon
    • Analytical Science and Technology
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    • v.14 no.2
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    • pp.159-166
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    • 2001
  • A humic acid(HA, Aldrich Co) sample was subjected to ultrafiltration for molecular size fractionation and three fractions of different nominal size($F_1$: 1,000-10,000 daltons; $F_2$: 10,000-50,000 daltons; $F_3$: 100,000-300,000 daltons) were obtained. The structural characteristics of the size-fractionated HA were analyzed using their IR and solid state C-13 NMR spectral data, and the carboxylate group contents of the humic acids were determined using their pH titration data. The $^7F_0-{^5}D_0$ excitation spectra of Eu(III) complexes of the size-fractionated mgHA in aqueous solution were acquired($[Eu(III)]=1.0{\times}10^{-4}mol\;L^{-1}$, $(HA)=470-970mg\;L^{-1}$) at pH 5.0 using a pulsed tunable laser system, in which metal binding properties of the size-fractionated HA were elucidated and compared on another. Characterization of the IR and C-13 NMR spectral data indicated that the fraction($F_3$) with molecules of larger size were primarily aliphatic, while the fractions($F_1$, $F_2$) with smaller molecules of less than 50,000 daltons were predominantly aromatic. Titration data were consistent with an increase in the number of carboxylate groups per unit mass as molecular size became smaller. The $^7F_0-{^5}D_0$ excitation spectral data of Eu(III)-humate complexes showed that the peak maxima on these spectra were shifted toward lower energies with increasing molecular size of HA, indicating the higher degree of bindings of the Eu in the molecules of larger size. We also discussed the relationship of the lower energy shifts of the maximum peaks with increasing the molecular size of HA with the structural differences of the size-fractionated HA.

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A Study on the Correlations between Molecular Structures of Soil Humins and Sorption Properties of Phenanthrene (토양 휴민(Humin)의 분자구조 특성과 Phenanthrene 흡착상수와의 상관관계에 대한 연구)

  • Lee, Doo-Hee;Eom, Won-Suk;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.12
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    • pp.897-905
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    • 2013
  • In this study, sorption coefficients (${\log}K_{OC}$, n) for the binding of phenanthrene (PHE) to soil humins, insoluble fraction of soil humc substances (HS), were determined and relationship between the sorption coefficients and structural characteristics of the soil humins were investigated. The soil humins used in the present study were isolated from 7 different soils including 5 domestic soils, an IHSS standard and a peat soil, and characterized by elemental analysis and CPMAS $^{13}C$ NMR method. $^{13}C$ NMR spectral features indicate that the soil humins are mainly made up of aliphatic carbons (57.1~72.3% in total carbon) with high alkyl-C moiety, and the alkyl-C contents ($C_{Al-H,C}$, %) was in order of granite soil Hu (26~42%) > volcanic ash soil, HL Hu (23.9%) > Peat Hu (14.0%). The results of correlation study show that a positive relationship ($r^2$ = 0.77, p < 0.05) between organic carbon normalized-sorption coefficients ($K_{OC}$, mL/g) and alkyl-C contents($C_{Al-H,C}$, %), while negative relationship ($r^2$ = (-)0.74, p < 0.05) between Freundlich sorption parameter (n) and H,C-substituted aromatic carbon contents ($C_{Ar-H,C}$, %). The magnitude of $K_{OC}$ values are also negatively well correlated with polarity index (e.g., PI, N + O)/C) ($r^2$ = (-)0.74, p < 0.1). These results suggest that the binding capacity (e.g., $K_{OC}$) for PHE is increased in soil humin molecules having high contents of alkyl-C or lower polarity, and nonlinear sorption for PHE increased as the H,C-substituted aromatic carbon contents ($C_{Ar-H,C}$, %) in the soil humins increased. The PHE sorption characteristics on soil humins are discussed based on the dual reactive mode of sorption model.

Studies on the Michael Addition Reaction between Secondary Amino Groups on the Silica Surface with Poly(ethylene glycol) Diacrylates (실리카 나노입자 표면에 결합된 2차 아미노기와 Poly(ethylene glycol) Diacrylate의 마이클 부가반응에 대한 연구)

  • Jeon, Ha Na;Ha, KiRyong
    • Polymer(Korea)
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    • v.36 no.6
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    • pp.822-830
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    • 2012
  • We used dipodal type bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to modify silica nanoparticles to introduce secondary amino groups on the silica surface. These N-H groups were reacted with three different molecular weights (M.W. = 258, 575, and 700) of poly(ethylene glycol) diacrylates to introduce different attached layer thicknesses on the silica surface by Michael addition reaction. After Michael addition reaction, we used several analytical techniques such as fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state $^{13}C$ cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy to characterize introduced structures. We found almost complete Michael addition reaction of both two acrylate groups of PDGDA with N-H groups of BTMA modified silica to form ${\beta}$-amino acid esters. Between equimolar ratio of pure BTMA and pure PEGDA reaction, only one acrylate group of two acrylate groups of PEGDA reacted with N-H groups of pure BTMA to form ${\beta}$-amino acid ester and the other remaining acrylate group can be used to form a polymer later.

Synthesis of Aluminophosphate using Structure Directing Agent containing Piperidine Moiety: Effect of SDA on Crystal Structure (피페리딘 구조유도분자를 이용한 알루미노포스페이트 제올라이트 합성: 피페리딘 구조유도분자가 결정구조 형성에 미치는 영향)

  • Shin, Hye Sun;Jang, Ik Jun;Shin, Na Ra;Ju, Bit Na;Cho, Sung June
    • Korean Chemical Engineering Research
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    • v.49 no.5
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    • pp.657-663
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    • 2011
  • Structure directing agent(SDA) containing piperidine moiety such as piperidine(PI), 2-methylpiperidine (MPI), 2,6-dimethylpiperidine(DMPI) and 2,2,6,6,-tetramethylpiperidine(TMPI), respectively has been utilized to synthesize aluminophosphate zeolite using hydrothermal method. The gel composition was $1.0Al_2O_3:1.0P_2O_5:0.76SDA:45H_2O$ and the hydrothermal heating was performed in an oven at 443 K and for 7 days at static mode. The obtained zeolitic material contained a lamellar structure when PI was used as the SDA. With a progressive increase of the SDA size, various structures of aluminophosphate including AlPO-5 of AFI structure were obtained. The aluminophosphate of SAS structure was formed when the largest TMPI was utilized as the SDA, which was confirmed by the Rietveld refinement. The result of $^{27}Al$ and $^{31}P$ MAS NMR of the sample suggested that Al and P were incorporated into the framework of the aluminophosphate.

Effects of Residual Solvents in the Phase Transition, Transition Enthalpy, and Transition Temperature of Phospholipid Membranes (잔류 유기 용매가 모델 세포 지질막의 상전이, 상전이 엔탈피 및 상전이 온도에 미치는 영향)

  • An, Eun Seol;Choi, Jae Sun;Lee, Dong Kuk
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.40 no.2
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    • pp.163-170
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    • 2014
  • Lipid membranes composed of phosphatidylcholine (PC) are used in biophysical study to mimic cellular membranes and interactions between the membrane and chemicals, where organics solvents are used in dissolving lipids or chemicals. Later, solvents are removed from the solution under nitrogen gas at room temperature, followed by the further removal of the solvent at vacuum condition for several hours. In this process, some solvents are easily removed under described conditions above and others are required more severe conditions. In this study, $^{31}P$ solid-state nuclear magnetic resonance (SSNMR) techniques and differential scanning calorimetry (DSC) were used to see any changes in the line shapes of $^{31}P$ NMR spectra of multilamellar vesicles (MLVs) samples of POPC and in the phase change temperature of multilamellar vesicles (MLVs) of DPPC in DSC thermogram with or without any residual solvents. The thermodynamic parameters associated with the solvents did exhibit noticeable changes depending on solvent types. Thus, it is concluded that solvents should be carefully chosen and removed completely and experimental results should also be interpreted with caution particularly for the experiments investigating lipid phase changes and related topics.

Complex Formation of Transition and Post-Transition Metal Ions with 1,15-Diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane (전이 및 중금속이온과 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxa-cyclooctadecane과의 착물형성)

  • Kim, Si-Joong;Lee, Myung-Jae;Koo, Chang-Hyung;Woo, Kyoun-Ja
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.645-652
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    • 1991
  • The stability constants$(K_f)$ of the complexes of some transition and post-transition metal ions (Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Hg(Ⅱ)) with $N_2O_3$-donor macrocyclic ligand, 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane ($NtnOdienH_4$), have been determined by potentiometry in aqueous solution at $25^{\circ}C$. Log $K_f$ values of the complexes were : Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Pb(Ⅱ) : 6.65, and Hg(Ⅱ) : 14.87. The order of stabilities of transition metal complexes was the same as the natural order of stability proposed by Williams-Irving. In post-transition metal complexes, the order of stabilities was Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ), and the covalent character in metal ion-donor atoms bonds appeared a dominant factor in the stability. In methanol solution, each metal ion forms 1 : 1 complex, while Ni(Ⅱ) ion forms both 1 : 1 and 1 : 2 complexes. It was confirmed by $^1H-$ and $^{13}C-$NMR spectral study that the nitrogen atoms in the ligand were major contributors for the complexation of post-transition metal ions with the ligand. It was shown, by elementry analysis, electrical conductivity and magnetic susceptibility measurements, and spectral analysis, that solid Cu(Ⅱ)-and Zn(Ⅱ)-complexes have a distorted octahedral and a tetrahedral structure, respectively.

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