• Elastomers and Composites
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• 제52권3호
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• pp.180-186
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• 2017

In this work, the effect of low-temperature dehydration of a poly(styrene-co-styrenesulfonic acid) (PSSA) membrane was investigated by differential scanning calorimetry, fourier transform infrared spectroscopy (FT-IR), electron magnetic resonancespectroscopy (EMR), and $^1H$- and $^{13}C$ solid-state nuclear magnetic resonance spectroscopy. These analyses were performed at room temperature for powdered PSSA specimens with and without dehydration and the following key observations were made. First, FT-IR analysis showed that low-temperature dehydration not only transformed the [${SO_3}^-{\cdots}H^+$] ionic pair in the non-hydrated PSSA to an $SO_3H$ group, but also induced the formation of -C=C- double bonds in the dehydrated PSSA. Second, the ${-SO_3}^{\bullet}$ radical was unambiguously identified by EMR spectroscopy. Third, H-abstraction was detected by $^1H$ magic-angle spinning spectroscopy. Finally, an unexpected color shift from white for the non-hydrated PSSA to a yellowish brown for the dehydrated sample was observed. In order to explain these experimental results, it was proposed that the formation of the intermediate hydrogen ($H^{\bullet}$) or hydroxyl radical ($HO^{\bullet}$) species was initiated by the dehydration process. The sespecies attacked the $SO_3H$ group and the tertiary proton at the ${\alpha}-carbon$, resulting in the formation of $-SO^{\bullet}$ radicals and -C=C- double bonds, which correlated with the color shift in the dehydrated PSSA sample. The semechanisms are useful for understanding the simultaneous loss of an aromatic ring and -SO- groups in the PSSA fuel cell membrane.

• 공업화학
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• 제10권7호
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• pp.1020-1027
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• 1999

헤테로폴리산(HPW)을 표면적이 서로 다른 담체인 $SiO_2$ MCM-41, MCM-48에 담지농도와 소성온도를 달리하며 담지시켰다. X-선 회절분석, 질소 흡착법, 적외선 흡수 스펙트럼, $^{31}P$ 고체 핵자기 공명을 통해서 이 담지촉매의 특성을 조사하였다. IR과 NMR의 결과로부터 HPW가 담체안에서 케긴 구조를 유지하면서 존재함을 확인할 수 있었다. MCM-41의 경우에는 35 wt %, MCM-48의 경우에는 65 wt %로 담지시킨 경우에도 X-선 회절패턴에서 HPW 고유의 피크가 나타나지 않았으며, 이와 같은 특성을 통해서 HPW가 고분산 되어 있음을 알 수 있었다. Di, bis, tri-pentaerythritol의 가수분해 반응에서 이들 담지 촉매는 높은 촉매 활성을 보였으며 HPW, $HPW/SiO_2$보다 HPW/MCM-41, 48의 촉매 활성이 더 우수하였다.

• 한국세라믹학회지
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• 제39권3호
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• pp.272-277
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• 2002

전구체로 ($NH_4)[Al(ethylenediaminetetraacetate)]{\cdot}2H_2O$ 착물을 이용한 수정된 열탄소환원질화법으로 질화알루미늄(AlN) 분말과 휘스커를 합성하였다. 이 분말은 질소분위기에서 별도의 환원용 탄소를 혼합하지 않고 1200$^{\circ}$C에서 1500$^{\circ}$C까지의 온도에서 하소시킨 다름 잔류탄소를 태워 버림으로써 얻어졌다. 이 질화과정을 Al-27 마법각 스핀 핵자기공명, 적외선 분광법 및 X-선 회절법으로 연구했다. 전구체 착물은 열분해되어 ${\rho}$-알루미나와 ${\gamma}$-알루미나로 되었다가 ${\gamma}-{\alpha}$알루미나 전이없이 AlN으로 바뀌었다. ${\gamma}$-알루미나가 AlN으로 바뀌면서 분말의 형상이 유지되는 것으로 보아 이 변환과정에서의 중간체는 알루미늄이나 aluminum suboxides와 같은 기체상이 아니고, 고체상의 $AlO_xN_y$임을 알 수 있다. (0001) 사파이어를 이용하면 AlN 휘스커를 합성할 수 있다.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.2021-2026
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• 2011

AgNPs (silver nanoparticles) has been widely used for the commercial products, which have antimicrobial agent, medical devices, food industry and cosmetics. Despite, AgNPs have been reported as toxic to the mammalian cell, lung, liver, brain and other organs and many researchers have investigated the toxicity of AgNPs. In this study, we investigated toxicity of the AgNPs to the liver cell using metabolomics based on HRMAS NMR (High Resolution Magic Angle Spinning Nuclear Magnetic Resonance) technics, which could apply to the intact tissues or cells, to avoid the sample destruction. Target profiling and multivariative statistical analysis were performed to analyze the 1D $^1H$ spectrum. The results show that the concentrations of many metabolites were affected by the AgNPs in the liver cell. The concentrations of glutathione (GSH), lactate, taurine, and glycine were decreased and most of amino acids, choline analogues, and pyruvate were increased by the AgNPs. Moreover, the levels of the metabolites were recovered upto similar level of metabolites in the normal cell by the pre-treatment of NAC, external antioxidant. The results suggest that the depletion of the GSH by the AgNPs might induce the conversion of lactate and taurine to the pyruvate.

• 한국광물학회지
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• 제13권4호
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• pp.186-195
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• 2000

To study phosphate adsorption on kaolinite, $^{31}$ P MAS NMR(magic angle spinning nuclear magnetic resonance spectroscopy)has been used for kaolinite reacted in 0.1 M phosphate solutions at pH’s from 3 to 11. There are at least 3 different forms of phosphate on kaolinite. One is the phosphate physically adsorbed on kaolinite surface (outer-sphere complexes) or species left after vacuum-filtering. The second is the phosphate adsorbed by ligand exchange (inner-sphere complexes), and the third is Al-phosphate precipitates which are pH dependent. Most of the inner-spherer complexes and surface precipitates are mainly on hydroxided Al(aluminol) rather than hydroxided Si(silanol). These are pertinent with the results obtained from the phosphate adsorption experiments on silica gel and ${\gamma}$-Al$_2$O$_3$ as model compounds, respectively. The two peaks with more negative chemical shifts(more shielded) than the ortho-phosphate peak (positive chemical shift) are assigned to be the inner-sphere complexes and surface precipitates. The $^{31}$ P chemical shifts of the Al-phosphate precipitates are more negative than those of inner-sphere complexes at a given pH due to the larger number of P-O-Al linkages per tetrahedron. The chemical shifts of both the inner-sphere complexes and surface precipitates are more negative than those of inner-sphere complexes at a given pH due to the larger number of P-O-Al linkages per tetrahedron. The chemical shifts of both the inner-sphere complexes and surface precipitates become progressively less shielded with increasing pH. For the inner-sphere complexes, decreasing phosphate protonation combined with peak averaging by rapid proton exchange among phosphate tetrahedra with different numbers of protons is though to be the reason for the peak change. The decreasing shielding with increasing pH for surface precipitates is probably due to the decreasing average number of P-O-Al linkages per tetrahedron combined with decreasing protonation like inner-sphere complexes.

• 대한화학회지
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• 제37권10호
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• pp.867-873
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• 1993

결정화 시간 및 반응 혼합물내의 $H_2O/Al_2O_3$의 비가 AlPO$_4$-5 분자체의 합성에 미치는 영향을 X-선 회절(XRD), 질소흡착실험, 전자현미경(SEM) 그리고 고체상 $^{27}$Al nuclear magnetic resonance(NMR)를 사용하여 조사하였다. 반응온도가 150$^{\circ}$C일 때 AlPO$_4$-5의 결정화 시간에 따른 결정성은 S자형 곡선을 보였으며, 유도기간(induction period)은 1시간 이내인 것으로 나타났다. 반응물에서 생성물, AlPO$_4$-5로의 전환을 명확히 관측할 수 있었으며 약 2시간의 결정화 전후 측정된 모든 물성은 큰 변화를 보였다. 반응물내의 $H_2O/Al_2O_3$의 비가 증가함에 따라 다결정의 AlPO$_4$-5는 육각기둥 모양의 단결정으로 변화하였으며 얻어진 결정의 길이/너비의 비는 증가하였다.

• Bulletin of the Korean Chemical Society
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• 제30권3호
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• pp.608-612
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• 2009

The local structures of the boron and vanadium sites in the ternary glass $xV_2O_5-B_2O_3-yNa_2O$ were studied by $^{11}B\;and\;^{51}V$ magic angle spinning (MAS) nuclear magnetic resonance (NMR). With increasing x, the mole ratios of the $BO_3\;and\;BO_4$ structures were enhanced, as were the quadrupole asymmetry parameters for the $BO_3$ structures, while the quadrupole coupling constants for the sites were reduced. However, the opposite trends were observed with increasing y, implying that $V_2O_5$ and $Na_2O$ play opposite roles. The $VO_4,\;VO_5\;and\;VO_6$ structures with all oxygens bonded to the vanadium neighbors were identified. Vanadiums bonded to the greater number of oxygens were more populated at higher contents of $Na_2O\;and\;V_2O_5$. In addition, the $VO_4$ structures with at least one oxygen bonded to boron instead of vanadium were detected at low $Na_2O$ contents. The electron densities of various vanadium oxide structures were affected by the weight densities and vanadium ion densities. The $VO_4$ structures were more likely to be vanadium oxide structures right next to $V4^{+}$ ions.

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.999-1004
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• 2007

Spherical porous silica supports modified with titanium or zirconium alkoxides were prepared, and allyl groups were chemically attached to the titanized or zirconized silica supports, and the product was cross-polymerized with a double bond containing cellulose derivative to yield new CSPs (chiral stationary phases). Magic angle spinning 13C solid state NMR and elemental analysis were used to characterize the CSPs. The performances of the chiral stationary phases were examined in comparison with a conventional chiral stationary phase. Spherical porous silica particles modified with 3,5-dimethylphenylcarbamate of cellulose were prepared and used as the conventional chiral stationary phase. Chromatographic data were collected for a few pairs of enantionmers in heptane/2-propanol mixed solvents of various compositions with the three chiral columns and the results were comparatively studied. The separation performance of the chrial phase made of the titanized silica was better than the others, and the separation performance of the chiral phase of the zirconized silica was comparable to that of the conventional chiral phase. The superiority of titanized silica over bare or zirconized silica in chiral separation seemed to be owing to the better yield of crosslinking (monitored by increase of carbon load) for titanized silica than for the others.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.934-942
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• 1998

$^13CO$ chemisorbed on platinum particles in L-zeolite has been investigated by static and magic angle spinning NMR spectroscopy. The representative spectra are composed of a broad asymmetric peak with a center of gravity at 230±30 ppm and a sharp symmetric peak at 124±2 ppm which is tentatively assigned to physisorbed $CO_2$, on inner walls of L-zeolite. Overall, the broad resonance component is similar to our previous results of highly dispersed (80-96%) CO/Pt/silica or CO/Pt/alumina samples, still showing metallic characters. The principal difference is in the first moment value. The broad peak in the spectra is assigned to CO linearly bound to Pt particles in the L-zeolites, and indicates a distribution of isotropic shifts from bonding site to bonding site. The NMR results reported here manifest that the Pt particles inside of the L-zeolites channels are not collectively the same with the ones supported on silica or alumina with similar dispersion in terms of Pt particle shape and/or ordering of Pt atoms in a particle. As a result, Pt particles of CO/Pt/L-zeolite were agglomerated accompanying CO desorption upon annealing. There were no definite changes in the NMR spectra due to differences of exchanged cations. Comparison of our observation on CO/Pt/L-zeolite with Sharma et al.'s reveals that even when the first moment, the linewidtb, and the relaxation times of the static spectra and the dispersion measured by chemisorption are similar, the properties of Pt particles can be dramatically different. Therefore, it is essential to take advantage of the strengths of several techniques together in order to interpret data reliably, especially for the highly dispersed samples.

• 한국자기공명학회논문지
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• 제22권4호
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• pp.91-100
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• 2018

Benzisothiazolinone (BIT) is the preservative that is widely used in industrial and household products. In this study, zebrafish (Danio rerio) was exposed to BIT at different concentrations (control, 0.5 g/L, 1.0 g/L and 2.0 g/L) for 72 hours. The techniques of nuclear magnetic resonance (NMR) spectroscopy were applied to analyze the effects of BIT on zebrafish. The advantages of NMR are the minimal sample preparation and high reproducibility of experimental results. With the multivariate statistical analysis, dimethylamine, N-acetylaspartate, glycine and histidine were identified as an important metabolite in differentiating between the control and BIT-exposed group. This study will improve the understanding the metabolite changes in the zebrafish in response to BIT exposure.