• Title/Summary/Keyword: Reaction mechanisms

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Solution Phase Photolyses of Substituted Diphenyl Ether Herbicides under Simulated Environmental Conditions (모조(模造) 환경조건하(環境條件下)에서의 치환(置換) Diphenyl Ether 제초제(除草劑)의 광분해(光分解)에 관(關)한 연구(硏究))

  • Lee, Jae-Koo
    • Applied Biological Chemistry
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    • v.17 no.3
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    • pp.149-176
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    • 1974
  • Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

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Anti-inflammatory effect of Sinhyowoldo-san Extract with regard to Pro-inflammatory Mediators in PMA plus A23187-induced Human Mast Cells (인간 비만세포에서 PMA와 A23187에 의해 유도된 전염증 매개체에 대한 신효월도산 추출물의 항염증 효과)

  • Wi, Gyeong;Yang, Da-Wun;Kang, Ok-Hwa;Kim, Sung-Bae;Mun, Su-Hyun;Seo, Yun-Soo;Kang, Da-Hye;Lim, Jae-Soo;Kim, Ma-Ryong;Kwak, Nam-Won;Kong, Ryong;Kwon, Dong-Yeul
    • The Korea Journal of Herbology
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    • v.29 no.6
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    • pp.117-123
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    • 2014
  • Objectives : Sinhyowoldo-san (SHWDS) is said to be a traditional medicine used for shigellosis, abdominal pain, diarrhea. But mechanism of SHWDS mediated-modulation of immune function is not sufficiently understood. To ascertain the molecular mechanisms of SHWDS 70% EtOH extract on pharmacological and biochemical actions in inflammation, we researched the effect of pro-inflammatory mediators in phorbol-12-myristate-13-acetate (PMA)+ A23187-activated human mast cell line (HMC-1). Methods : In the present research, cell viability was measured by MTS assay. pro-inflammatory cytokine production was measured by performing enzyme-linked immunosorbent assay (ELISA), reverse transcription polymerase chain reaction (RT-PCR), and western blot analysis to analyze the activation of mitogen-activated protein kinases (MAPKs), nuclear factor kappa-light-chain-enhancer of activated B cells ($NF-{\kappa}B$). The investigation focused on whether SHWDS inhibited the expressions of interleukin-6 (IL-6), interleukin-8 (IL-8), MAPKs and $NF-{\kappa}B$ in PMA+A23187-activated HMC-1 cells. Results : SHWDS has no cytotoxicity at measured concentration (50, 100, and $250{\mu}g/ml$). SHWDS ($250{\mu}g/ml$) inhibits pro-inflammatory cytokine expression in PMA+ A23187-activated HMC-1 cells. Moreover, SHWDS inhibited cyclooxygenase (COX)-2 expression. In activated HMC-1 cells, SHWDS suppressed phosphorylation of extracellular signal-regulated kinase (ERK 1/2) and c-jun N-terminal Kinase (JNK 1/2). Then, SHWDS suppressed activation of nuclear factor $NF-{\kappa}B$ in nuclear, degradation of IkB ${\alpha}$ in cytoplasm. Conclusions : We propose that SHWDS has an anti-inflammatory therapeutic potential, which may result from inhibition of ERK 1/2, JNK 1/2 phosphorylation and $NF-{\kappa}B$ activation, thereby decreasing the expression of pro-inflammatory genes.

MMP-1 and TIMP-1 production in MG-63 cells stimulated with Prevotella nigrescens Lipopolysaccharide (Prevotella nigrescens lipopolysaccharides로 자극된 MG63 세포에서 분비되는 기질금속단백질 MMP-1과 TIMP-1의 수준에 관한 연구)

  • Yang Won-Kyung;Kim Mi-Ri;Shon Won-Jun;Lee In-Bog;Cho Byeong-Hoon;Um Chung-Moon;Son Ho-Hyun
    • Restorative Dentistry and Endodontics
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    • v.29 no.5
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    • pp.470-478
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    • 2004
  • The purpose of this study is to monitor the secretion of matrix metalloproteinase-1 (MMP-1) and tissue inhibitor of metalloproteinase-1 (TIMP-1) produced by human osteosarcoma cell line (MG63) stimulated with Prevotella nigrescens lipopolysaccharides (LPS). and to compare the level of secretion before and after the treatment of calcium hydroxide on P. nigrescens LPS. LPS was extracted and purified from anaerobically cultured P. nigrescens. MG63 cells were stimulated by the LPS (0, 1, $10{\;}\mu\textrm{g}/ml$) or LPS($10{\;}\mu\textrm{g}/ml$) pretreated with 12.5 mg/ml of $Ca(OH)_2$ for 3 days. Total RNA was isolated from the cell. and real-time quantitative polymerase chain reaction (PCR) was performed for quantification of MMP-1 and TIMP-1. The results were as follows. 1. MMP-1 mRNA expression at 48 hr was highly increased by stimulation with P. nigrescens LPS. The increase was dose-dependent. 2. When stimulated with ($1{\;}\mu\textrm{g}/ml$ of LPS. TIMP-1 mRNA expression was highly increased at 24 hr and 48 hr. However. TIMP-1 expression was suppressed at higher concentration ($10{\;}\mu\textrm{g}/ml$). 3. When P. nigrescens LPS was pretreated with $Ca(OH)_2$. MMP-1 and TIMP-1 gene expression was downregulated. The results of this study suggest that transcriptional regulation of MMP-1 and TIMP-1 by P. nigrescens LPS could be one of the important mechanisms in bone resorption of periapical inflammation. The result of calcium hydroxide on MMP-1 and TIMP-1 gene expression suppression shows that calcium hydroxide detoxified bacterial LPS and thus should be used the medication of choice for intracanal dressings in root canal infected with black-pigmented bacteria.

A Set of Anthocyanin Biosynthetic Genes are Differentially Expressed in Strawberry (Fragaria x ananassa cv Maehyang) during the Fruit Development Process (매향 딸기로부터 anthocyanin 합성 유전자의 분리 및 과실발달 과정에서의 발현 분석)

  • Bae, Ki-Suk;Kih, Joon-Yeong;Pyee, Jae-Ho
    • Journal of Life Science
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    • v.18 no.2
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    • pp.234-240
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    • 2008
  • Anthocyanin synthesis in strawberry (Fragaria x ananassa cv Maehyang) begins approximately 26 days postflowering and continued throughout fruit ripening. A set of cDNA clones encoding the anthocyanin biosynthetic enzymes were isolated from strawberry. A pair of primers were designed for polymerase chain reaction (PCR) through the comparison of the nucleotide sequences of homologous genes from diverse plants. Reverse transcriptase-PCRs were performed using cDNA synthesized from ripe fruit total RNA and the primers corresponding to each gene. Eight genes of the anthocyanin pathway were cloned and confirmed by sequencing to code for phenylalanine ammonia lyase (PAL), 4-cummarate CoA ligase (4CL), chalcone synthase (CHS), chalcone isomerase (CHI), flavanone-3-hydroxylase (F3H), dihydroflavonol 4-reductase (DFR), anthocyanidine synthase (ANS), UDP-glucose:flavonoid-3-O-glucosyl-transferase (UFGT). Northern analyses showed that the corresponding genes were differentially expressed during the fruit development process. All genes except PAL were predominantly expressed in fruit. Expression of PAL, DFR and ANS was detected 10 days postflowering at the early stage of fruit development, declined for a while and sharply increased 22 days postflowering then showed a peak 34 days postflowering. The other genes, however, were not expressed up to 22 or 30 days postflowering when the initial fruit ripening events occur at the time of initiation of anthocyanin accumulation. The onset of anthocyanin synthesis in ripening strawberry coincides with a coordinated induction of the anthocyanin pathway genes, suggesting the involvement of regulatory genes. We propose that at least two different regulatory mechanisms playa role in the biosynthesis of anthocyanin during color development of strawberry.

Experimental Models of Schizophrenia (정신분열병의 실험적 모델)

  • Cheon, Jin-Sook
    • Korean Journal of Biological Psychiatry
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    • v.6 no.2
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    • pp.153-160
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    • 1999
  • Animal models can provide a useful tool for the study of some aspects of psychiatric disorders and their treatment. The four criteria for the evaluation of animal models of psychiatric disorders are as following : 1) similarity of inducing conditions 2) similarity of behavioral state 3) common underlying neurobiological mechanisms 4) reversal by clinically effective treatment techniques. Several animal models have been proposed for schizophrenia : phenylethylamine model, L-dopa model, hallucinogen model, cocaine model, amphetamine model, phencyclidine model, noradrenergic reward system lesion model, reticular stimulation model, social isolation model, conditioned avoidance reaction, catalepsy test, paw test, self-stimulation paradigms, latent inhibition paradigms, blocking paradigms, prepulse inhibition of the startle reflex, rodent interaction, social behavior in monkeys, hippocampal damage, high ambient pressure, and models using selective breeding. Among them, animals with bilateral lesion of the hippocampus may provide an adequate animal model for several symptoms of schizophrenia, and ketamine model can reproduce negative symptoms and cognitive deficits as well as positive symptoms of schizophrenia. In conclusion, no model of schizophrenia is entirely representative of the disease, and findings gleaned from model systems must be cautiously interpreted. Furthermore, the process of developing and validating animal models must work in concert with the process to identify reliable measures of human phenomenology.

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Oxidative Stress-dependent Structural and Functional Regulation of 2-cysteine Peroxiredoxins In Eukaryotes Including Plant Cells (산화 스트레스에 의존한 식물 및 진핵세포 2-시스테인 퍼록시레독신의 기능 조절)

  • Jang, Ho-Hee;Kim, Sun-Young;Lee, Sang-Yeol
    • Journal of Plant Biotechnology
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    • v.33 no.1
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    • pp.1-9
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    • 2006
  • Peroxiredoxins (Prxs) are ubiquitously distributed and play important functions in diverse cellular signaling systems. The proteins are largely classified into three groups, such as typical 2-Cys Prx, atypical 2-Cys Prx, and 1-Cys Prx, that are distinguished by their catalytic mechanisms and number of Cys residues. From the three classes of Prxs, the typical 2-Cys Prx containing the two-conserved Cys residues at its N-terminus and C-terminus catalyzes $H_2O_2$ with the use of thioredoxin (Trx) as an electron donor. During the catalytic cycle, the N-terminal Cys residue undergoes a peroxide-dependent oxidation to sulfenic acid, which can be further oxidized to sulfinic acid at the presence of high concentrations of $H_2O_2$ and a Trx system containing Trx, Trx reductase, and NADPH. The sulfinic acid form of 2-Cys Prx is reduced by the action of sulfiredoxin which requires ATP as an energy source. Under the strong oxidative or heat shock stress conditions, 2-Cys Prx in eukaryotes rapidly switches its protein structure from low-molecular-weight species to high-molecular-weight protein structures. In accordance with its structural changes, the protein concomitantly triggers functional switching from a peroxidase to a molecular chaperone, which can protect its substrate denaturation from external stress. In addition to its N-terminal active site, the C-terminal domain including 'YF-motif' of 2-Cys Prx plays a critical role in the structural changes. Therefore, the C-terminal truncated 2-Cys Prxs are not able to regulate their protein structures and highly resistant to $H_2O_2$-dependent hyperoxidation, suggesting that the reaction is guided by the peroxidatic Cys residue. Based on the results, it may be concluded that the peroxidatic Cys of 2-Cys Prx acts as an '$H_2O_2$-sensor' in the cells. The oxidative stress-dependent regulation of 2-Cys Prx provides a means of defense systems in cells to adapt stress conditions by activating intracellular defense signaling pathways. Particularly, 2-Cys Prxs in plants are localized in chloroplasts with a dynamic protein structure. The protein undergoes conformational changes again oxidative stress. Depending on a redox-potential of the chloroplasts, the plant 2-Cys Prx forms super-molecular weight protein structures, which attach to the thylakoid membranes in a reversible manner.

Kinetics of Silica Sorption and Desorption in Soil as affected by pH and Temperature (pH 와 온도(溫度)에 따른 토양(土壤)의 규산(硅酸) 흡(吸) · 탈착(脫着)에 대(對)한 역학적(力學的) 연구(硏究))

  • Lee, Sang-Eun;Neue, Heins Ulitz
    • Korean Journal of Soil Science and Fertilizer
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    • v.25 no.4
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    • pp.342-356
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    • 1992
  • Kinetic studies using stirred-flow methods were conducted with the Luisiana soil at three pH levels(pH 5, 6.5, and 8) and three temperature levels(10, 25, and $40^{\circ}C$) to explore effects on the rate of silica retention and release and to find out reaction mechanisms. In this study the maximum silica retention could not be obtained for long enough experimental time. The silica sorption isorption was C type fitted well to Freundlich equation. The pH of the soil suspension increased by the silica release process at low pH treatments(pH 5 and 6.5), while decreased at high pH treatment(pH 8). From the above findings It can be deduced that the mechanism of silica retention is a multilayer forming process to change the ligand form depending on pH condition. In the proposed mechanism the sorbed silica provide new binding sites for additional sorption of silica, while the activation energy for the formation of subsequent layers increases correspondingly. The silica retention and release process were well described by first-order and parabolic diffusion equation. However, clear interpretation for silica sorption mechanism using these equations could not be made. The validity of the fraction term (Fa and Fd) included in first-order and parabolic diffusion equation requires further examinations because the temperature effect on apparent rate constant shows no constant trends among temperature treatments, while there was a good trend in Elovich and modified Freundlich equation where the fraction term was not included.

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Antioxidant activity and anti-tumor immunity by Propolis in mice

  • Choi, In-Sook;Itokawa, Yuka;Maenaka, Toshihiro;Yamashita, Takenori;Mitsumoto, Morihide;Tano, Kaoru;Kondo, Hiroyo;Ishida, Torao;Nakamura, Takashi;Saito, Kiyoto;Terai, Kaoru;Monzen, Hajime;Oshima, Masami;Takeuchi, Tetsuo;Mituhana, Yuicti;Bamen, Kenichi;Ahn, Kyoo-Seok;Gu, Yeun-Hwa
    • Advances in Traditional Medicine
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    • v.5 no.2
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    • pp.100-109
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    • 2005
  • In South America, natural products with unknown drug effects are used as folk remedies and for preventive medicine. Among South American natural products, we directed our attention to Propolis, which have been known as medicinal plants, and examined the mechanisms by which these substances affect antioxidant activity, anti-tumor activity and immunoresponse. When the antioxidant activities of Propolis were examined by the DPPH and Rhoudan iron methods, since Propolis contains high levels of flavonoids, it is thought that flavonoids may be responsible for the antioxidant activity in this study. In the examination of immunoenhancement activity, we measured lymphocyte versus polymorphonuclear leukocyte ratios (L/P activity). The number of lymphocytes was significantly increased in groups treated with Proplolis. Specifically, slightly high levels of $IFN-{\gamma}$ were measured in mice bearing the S-180 carcinoma, after administration of Propolis. This strongly suggests that cellular immunity is especially activated by treatment with Propolis, because production of $IFN-{\alpha}$ is limited to the T cells and NK cells stimulated by mitogen and sensitized antigen. $TNF-{\alpha}$ shows a different extent and mechanism of action depending on the target cells. When $TNF-{\alpha}$ was measured in mice bearing the S-180 carcinoma, mice treated with Propolis showed slightly higher $TNF-{\alpha}$ levels as compared to the control group. This suggests that activated macrophages produce $TNF-{\alpha}$ in mice treated with Prapolis, since activated macrophages and lymphocytes are the source of most $TNF-{\alpha}$. When anti-tumor action was examined using two kinds of sarcoma (Ehrlich solid carcinoma and Sarcoma-180 carcinoma), tumor-suppressive ratios after treatment with Propolis was 29.1%. When Sarcoma-180 solid carcinoma was used, tumor-suppressive ratios were 62%. Thus, Propolis showed strong anti-tumor activity against two kinds of solid carcinoma. Taken altogether, this strongly suggests that Propolis enhances original functions of macrophages and NK cells, and as a result, secondarily enhances the immune reaction and suppresses tumor growth.

AN IMMUNOHISTOLOGIC STUDY ON THE ACTIVITY OF MACROPHAGE AND T-CELL IN THE PERIODONTIUM DURING TOOTH MOVEMENT OF DOG (성견의 실험적 치아이동시 치주조직내 대식세포와 T-림파구의 활성에 관한 면역조직화학적 연구)

  • Park, Eui-Woong;Kim, Sang-Cheol;Kook, Yoon-A
    • The korean journal of orthodontics
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    • v.25 no.4
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    • pp.433-445
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    • 1995
  • Tooth movement, the phenomena and mechanisms of which are still controversial, can be considered as part of the result of the inflammatory processes. The purpose of this study was to examine the activity of macrophage and T-cell, playing important roles in the immune reaction, in the periodontal ligament of dog, in which experimental tooth movement was performed. Six one and half year-old dogs, a control and 5 experimentals, were studied. Light force (50-75g) was applied by placing open-coil spring between left mandibular premolars ; heavy force (250-300g), between right mandibular premolars. Experimental dogs were sacrificed at 12 hours, 1, 3, 7 and 14 days since force application, respectively. And the histologic and the immunohistochemical evaluation on the obtained tissue were performed, using $\alpha$-1-antichymotrypsin and CD3 antibodies. The results were as follows : 1. There were more inflammatory cell infiltrations in heavy force group than in light force group until 3 days. But from 7 dsays on, no difference was not observed between groups ; Such an infiltration was more evident at pressure side than at tension side. 2. Osteoclastic activity at pressure side began to be seen in 12 hours, increasing until 7 days. After then it decreased ; Such an activity was more evident in heavy force group than in light force group. 3. Tearing of periodontal ligament and vascular dilatation at tension side began to be seen in 12 hours, increasing until 3 days. After then it decreased ; Such an observation was more evident in heavy force group than in light force group, but there was no difference between groups in 14 days. 4. $\alpha$-1-antichymotrypsin expression in control group was positive, mainly in sulcular epithelium, but negative in periodontal membrane, pulp, bone cells. 5. $\alpha$-1-antichymotrypsin expression in experimental group was more positive in pressure side than in tension side ; The expression was a little more positive in cervical area of tooth until 3 days, but after 7days, it was more positive in apical area. 6. $\alpha$-1-antichymotrypsin expression in light force group began to be observed in 12 hours and reached to the greatest level in 7 days, after which it decreased ; In heavy force group, it was the greatest in 3 days, after which it decreased. 3 Expression in the periodontium was almost negative.

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Sorption of Arsenite Using Nanosized Mackinawite (FeS)-Coated Silica Sand (나노 크기 매킨나와이트로 코팅된 규사를 이용한 아비산염의 흡착)

  • Lee, Seungyeol;Kang, Jung Chun;Park, Minji;Yang, Kyounghee;Jeong, Hoon Young
    • Journal of the Mineralogical Society of Korea
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    • v.25 no.4
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    • pp.185-195
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    • 2012
  • Due to the high reduction and sorption capacity as well as the large specific surface area, nanosized mackinawite (FeS) is useful in reductively transforming chlorinated organic pollutants and sequestering toxic metals and metalloids. Due to the dynamic nature in its colloid stability, however, nanosized FeS may be washed out with the groundwater flow or result in aquifer clogging via particle aggregation. Thus, these nanoparticles should be modified such as to be built into permeable reactive barriers. This study employed coating methods in efforts to facilitate the installation of permeable reactive barriers of nanosized mackinawite. In applying the methods, nanosized mackinawite was coated on non-treated silica sand (NTS) and chemically treated silica sand (CTS). For both silica sands, the maximum coating of mackinawite occurred around pH 5.4, the condition of which was governed by (1) the solubility of mackinawite and (2) the surface charge of both silica and mackinawite. Under this pH condition, the maximum coating by NTS and CTS were found to be 0.101 mmol FeS/g and 0.043 mmol FeS/g respectively, with such elevated coatings by NTS likely linked with impurities (e.g., iron oxides) on its surface. Arsenite sorption experiments were performed under anoxic conditions using uncoated silica sands and those coated with mackinawite at the optimal pH to compare their reactivity. At pH 7, the relative sorption efficiency between uncoated NTS and coated NTS changed with the initial concentration of arsenite. At the lower initial concentration, uncoated NTS showed the higher sorption efficiency, whereas at the higher concentration, coated NTS exhibited the higher sorption efficiency. This could be attributed to different sorption mechanisms as a function of arsenite concentration: the surface complexation of arsenite with the iron oxide impurity on silica sand at the low concentration and the precipitation as arsenic sulfides by reaction with mackinawite coating at the high concentration. Compared to coated NTS, coated CTS showed the lower arsenite removal at pH 7 due to its relatively lower mackinawite coating. Taken together, our results indicate that NTS is a more effective material than CTS for the coating of nanosized mackinawite.