• Bulletin of the Korean Chemical Society
• /
• 제34권12호
• /
• pp.3681-3689
• /
• 2013

This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation $Hg^{2+}$ and $Pb^{2+}$ showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

• 대한미생물학회지
• /
• 제13권1호
• /
• pp.25-30
• /
• 1978

Serratia marcescens의 동정(同定)을 분리배지(分離培地)를 이용(利用)하여 간편(簡便)한 방법(方法)으로 시도하였던 바 prodigiosin 산생(産生)은 proline을 위시해서 각종(各種) amino acid, thiamine 및 nicotinic acid에 의해서 항진되지 않았으나 혈액평판배지(血液平板培地)에서 본(本) 균종(菌腫)은 시간(時間)의 경과(經過)에 따라 흑색조(黑色調)를 띤 집락(集落)을 형성(形成)하며 이는 일차적(一次的)인 분리기준(分離基準)으로 이용(利用)될 수 있을 것 같다. Tween 80 및 대두유(大豆油) 분해성(分解性은) 본(本) 균(菌)에서 양성(陽性)이며 동정(同定)에 이용(利用)될 수 있으나 특이반응(特異反應)이 아니다. 그러므로 마지막으로 oxidase 반응(反應), lactose 및 sucrose 발효시험이 본(本) 균종(菌腫)의 확정(確定)에 수반되어야 한다.

• 펄프종이기술
• /
• 제44권3호
• /
• pp.9-14
• /
• 2012

Formed fermentation inhibitors during acid saccharification leads to poor alcohol production based on lignocellulosic bio-alcohol production process. In this work, it is focused on the formation of fermentation inhibitors from xylan, which is influenced by reaction tempearature and time of acidic sacharifiaction of xylose and glucuronic acid. In second step of concentrated acid hydrolysis, part of xylose and glucuronic acid was converted to furfuraldehyde and formic acid by dehydration and rearrangement reactions. Furfural was form from xylose, which was highly sensitive to reaction temperature. Formic acid was come from both xylose and glucuronic acid, which supposed to main inhibitor in biobutanol fermentation. Reaction temperature of second hydrolysis was main variables to control the furfural and formic acid generation. Careful control of acid saccharification can reduce generation of harmful inhibitors, especially second step of concentrated sulfuric acid hydrolysis process.

• Bulletin of the Korean Chemical Society
• /
• 제32권10호
• /
• pp.3644-3649
• /
• 2011

Multinuclear solid-state nuclear magnetic resonance (NMR) experiments were performed to investigate the local structure changes of nanoporous silica during hydrothermal treatment and surface modification with 3-aminopropyltriethoxysilane (3-APTES). The nanoporous silica was prepared by sol-gel polymerization using inexpensive sodium silicate as a silica precursor. Using $^1H$ magic angle spinning (MAS) NMR spectra, the hydroxyl groups, which play an important role in surface reactions, were probed. Various silicon sites such as $Q^2$, $Q^3$, $Q^4$, $T^2$, and $T^3$ were identified with $^{29}Si$ cross polarization (CP) MAS NMR spectra and quantified with $^{29}Si$ MAS NMR spectra. The results indicated that about 25% of the silica surface was modified. $^1H$ and $^{29}Si$ NMR data proved that the hydrothermal treatment induced dehydration and dehyroxylation. The $^{13}C$ CP MAS and $^1H$ MAS NMR spectra of 3-APTES attached on the surface of nanoporous silica revealed that the amines of the 3-aminopropyl groups were in the chemical state of ${NH_3}^+$ rather than $NH_2$.

• Bulletin of the Korean Chemical Society
• /
• 제25권11호
• /
• pp.1635-1640
• /
• 2004

The cyclophanes 1a-d containing two benzo[b]furan rings connected by various bridges have been prepared and their binding behaviors with N-benzylphenethylammonium cation 2 were examined by NMR titration method. The successive alkylation reactions of 4-hydroxyl groups and then 2-hydroxyl groups of 2,4-dihydroxybenzophenonse gave macrocycles 5a-c. Photoirradiation of the macrocycles 5a-c with 350 nm mercury lamp followed by dehydration afforded the cyclophanes 1a-c. Hydrolysis of two ester groups pendant on a bridge of 1b produced the carboxyl group-containing cyclophane 1d. The cyclophane 1a having a p-xylene bridge showed 1 : 1 binding with 2 with the binding constant of $36{\pm}6M^{-1}$ in 3 : 1 $CDCl_3$/methanol-$d_4$ solvent, while 1b and 1c which have neutral flexible bridges exhibited no appreciable binding with 2. The disodium salt of 1d showed much higher binding affinity for 2 forming 1 : 1 and 1 : 2 complexes.

• 한국안전학회지
• /
• 제16권2호
• /
• pp.75-79
• /
• 2001

For handling and storage of reactive chemicals, the hazard evaluations have been extremely important. In the chemical industry, the most concerns are focused on the thermal harzards such as runaway reactions and thermal decompositions, which are mostly governed by thermodynamics and reaction kinetics or these reactive chemical in the system. This study no investigated the thermal decomposition characteristics of nitrophenylhydrazine isomers by using differential scanning calorimeter(DSC) and accelerating rate calorimeter(ARC). Experimental results showed that exothermic onset-temperatures in nitrophenylhydrazine(NPH) isomers were about 160-$210^{\circ}C$ by DSC and 100-$150^{\circ}C$ by ARC. The decomposition temperature acquired by ARC was about 50-$60^{\circ}C$ lower than that by DSC. Reaction heats were about 40-100cal/g by DSC and 330-750ca1/g by ARC. While ortho isomer of NPH show two distinct exothermic peaks, para isomer shows a single peak in DSC curves. The first exothermic peak for 2-NPH is mainly due to intramolecular dehydration forming 1-hydroxybenzotriazole(HOBT) and the second exothermic peak is mainly due to the decomposition of HOBT formed in the first step of decomposition. The exothermin peak in the DSC curve for 4-NPH is mainly due to dissociation of hydrazino and nitro groups.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2009년도 제38회 동계학술대회 초록집
• /
• pp.35-35
• /
• 2010

Understanding the mechanistic details of heterogeneous catalytic reactions will provide a way to tune the selectivity between various competing reaction channels. In this regard, catalytic decomposition of alcohols over the rutile $TiO_2$(110) surface as a model oxide catalyst has been studied to understand the reaction mechanism employing the temperature-programmed desorption (TPD) technique. The $TiO_2$(110) model catalyst is found to be active toward alcohol dehydration. We find that the active sites are bridge-bonded oxygen vacancies where RO-H heterolytically dissociates and binds to the vacancy to produce alkoxy (RO-) and hydroxyl (HO-). Two protons adsorbed onto the bridge-bonded oxygen atoms (-OH) readily react with each other to form a water molecule at ~500 K and desorb from the surface. The alkoxy (RO-) undergoes decomposition at higher temperatures into the corresponding alkene. Here, the overall desorption kinetics is limited by a first-order decomposition of intermediate alkoxy (RO-) species bound to the vacancy. We show that detailed analysis on the yield and the desorption temperatures as a function of the alkyl substituents provides valuable insights into the reaction mechanism. After the catalytic role of the oxygen vacancies has been established, we employed x-ray photoelectron spectroscopy to further study the surface electronic structure related to the catalytically active defective sites. The defect-related state in valence band has been related to the chemically reduced $Ti^{3+}$ defects near the surface region and are found to be closely related to the catalytic activity of the $TiO_2$(110) surface.

• 대한화학회지
• /
• 제55권4호
• /
• pp.612-619
• /
• 2011

1,2-diphenyl-4-butyl-3,5-pyrazolidinedione(phenylbutazone, PB)의 란탄(III) 착물을 합성하여 원소분석, 몰전기전도도 측정, IR, UV-Vis. 및 NMR 스펙트럼으로 특성을 조사하였다. 스펙트럼 데이터로부터 PB가 pyrazolidinedione 고리의 두 카르보닐 산소를 통해 이배위 및 일이온화 리간드로 배위됨을 규명하였다. 몰전기전도도 데이터로부터 이들 착물이 비전해질임을 규명하였다. 이들 착물의 열적 행동을 공기 중에서 TG 및 DTG로 연구한 결과, 탈수화, 열적 안전성 및 열분해에 관한 정보를 얻을 수 있었다. 최종 생성물은 해당 금속의 산화물로 밝혀졌다. 탈수화 및 분해 단계에 대한 열역학 및 반응속도 파라메터를 구하였다. 분해 단계에 대한 음의 엔트로피 값은 반응물보다 활성화 착물이 더 질서있는 구조를 갖는다는 것을 의미하며, 이때 반응은 정상보다 느렸다. 이러한 연구를 바탕으로 착물의 분자식이 $[Ln(PB)_3]{\cdot}5H_2O$(Ln=La 및 Ce) 그리고 $[Ln(PB)_3 (H_2O)_2]{\cdot}2H_2O$(Ln=Pr, Nd 및 Sm)임을 규명하였다.

• 한국응용과학기술학회지
• /
• 제8권1호
• /
• pp.59-67
• /
• 1991

The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.

• Journal of Ginseng Research
• /
• 제36권3호
• /
• pp.277-290
• /
• 2012

The metabolic profiles of Panax quinquefolius and its associated therapeutic values are critically affected by the repetitious steaming times. The times-dependent steaming effect of P. quinquefolius is not well-characterized and there is also no official guideline on its times of steaming. In this paper, a UPLC-Q-TOF-MS/MS method was developed for the qualitative profiling of multi-parametric metabolic changes of raw P. quinquefolius during the repetitious steaming process. Our method was successful in discriminating the differentially multi-steamed herbs. Meantime, the repetitious steaming-inducing chemical transformations in the preparation of black American ginseng (American ginseng that was subjected to 9 cycles of steaming treatment) were evaluated by this UPLC-Q-TOF-MS/MS based chemical profiling method. Under the optimized UPLC-Q-TOF-MS/MS conditions, 29 major ginsenosides were unambiguously identified and/or tentatively assigned in both raw and multi-steamed P. quinquefolius within 19 min, among them 18 ginsenosides were detected to be newly generated during the preparatory process of black American ginseng. The mechanisms involved were further deduced to be hydrolysis, dehydration, decarboxylation and addition reactions of the original ginsenosides in raw P. quinquefolius through analyzing mimic 9 cycles of steaming extracts of 14 pure reference ginsenosides. Our novel steaming times-dependent metabolic profiling approach represents the paradigm shift in the global quality control of multi-steamed P. quinquefolius products.