• Title/Summary/Keyword: Adducts

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Comparison of Photophysical and Photochemical Properties of Khellin and 8-Methoxypsoralen

  • Ho Kwon Kang;Eun Ju Shin;Sang Chul Shim
    • Bulletin of the Korean Chemical Society
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    • v.12 no.5
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    • pp.554-559
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    • 1991
  • The photophysical and photochemical properties of khellin were compared with those of 8-methoxypsoralen (8-MOP). Quantum yields of fluorescence and triplet formation decreases as solvent polarity increases, which is opposite to 8-MOP, and photocycloadditivity of khellin to olefins is much lower than that of 8-MOP. Electron ejection from khellin by laser flash was not observed, but observed from 8-MOP. As models of 4',5'-monoadducts of khellin or 8-MOP with thymine base, khellin<>dimethylfumarate 4',5'-monoadduct (KDF) was also compared with 8-MOP<>thymidine 4',5'-monoadduct (F-2) in those properties to give some insight on the second-step biadduct formation resulting in cross-links of DNA duplex. KDF and F-2 were very similar to khellin and 8-MOP in photophysical properties, respectively. However, KDF did not form adducts with various olefins, and thus it is thought that 2,3-double bond of chromone moiety in khellin is hardly reactive in contrast with 3,4-double bond of coumarin moiety in 8-MOP. These results indicate that khellin is fairly photostable compound, a poor type Ⅰ photodynamic sensitizer and producer of ${O_2}^{-}$ which is some cause of phototoxic erythemal reactions and undesirable side effects. Therefore khellin is safer to use than 8-MOP in photochemotherapy of some skin diseases. Although khellin is much less reactive than 8-MOP, khellin must be also a monofunctional drug. Since khellin is, however, as effective as 8-MOP in photochemotherapy of some skin diseases, it is suggested that khellin may be different from 8-MOP in the action mechanism.

Trapping of Methylglyoxal by Sieboldin from Malus baccata L. and Identification of Sieboldin-Methylglyoxal Adducts Forms

  • Kim, Ji Hoon;Zhang, Kaixuan;Lee, Juhee;Gao, En Mei;Lee, Yun Jung;Son, Rak Ho;Syed, Ahmed Shah;Kim, Chul Young
    • Natural Product Sciences
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    • v.27 no.4
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    • pp.245-250
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    • 2021
  • The methylglyoxal (MGO) trapping constituents from Malus baccata L. were investigated using incubation of MGO and crude extract under physiological conditions followed by HPLC analysis. The peak areas of MGO trapping compounds decreased, and their chemical structures were identified by HPLC-ESI/MS. Sieboldin was identified as a major active molecule representing MGO-trapping activity of the crude extract. After reaction of sieboldin and MGO, remaining MGO was calculated by microplate assay method using imine (Schiff base) formation of 2,4-dinitrophenylhydrazine (DNPH) and aldehyde group. After 4 h incubation, sieboldin trapped over 43.8% MGO at a concentration of 0.33 mM and showed MGO scavenging activity with an RC50 value of 0.88 mM for the incubation of 30 min under physiological conditions. It was also confirmed that sieboldin inhibited the production of advanced glycation end products (AGE) produced by bovine serum albumins (BSA)/MGO. Additionally, MGO trapping mechanism of sieboldin was more specifically identified by 1H-, 13C-, 2D NMR and, confirm to be attached to the position of C-3' (or 5').

Studies on the Electrochemical Properties of Oxygen Adducts Tetradentate Schiff Base Cobalt (Ⅱ) Complexes in Aprotic Solvents (Ⅱ) (비수용매에서 네자리 Schiff Base Cobalt (II) 착물들의 산소첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 2 보))

  • Ki-Hyung Chjo;Jin-Soon Chung;Heui-Suk Ham;Seoing-Seob Seo
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.192-202
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    • 1989
  • Tetradentate schiff bases cabalt (II) complexes; Co(SED) and Co(ο-BSDT) were synthesized and these complexes allowed to reaction with dry oxygen to form oxygen adduct cobalt(III) complexes such as $[Co(o-BSDT)(DMSO)]_2O_2,\;[Co(SED)(Py)]_2O_2\;and\;[Co(o-BSDT)(Py)]_2O_2$ in DMSO and pyridine solutions. It has been found that the oxygen adduct cobalt(III) complexes have hexacoordinated octahedral configuration with tetradentate schiff base cobalt(II), DMSO or pyridine and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1:2. The redox processes, were investigated for Co(SEDT) and Co(ο-BSD) complexes in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine by cyclic voltammetry with glassy carbon electrode. As a result the redox processes of Co(II)/Co(III) and Co(II)/Co(I) found to be reversible or quasi-reversible for non uptake oxygen complexes but oxygen adduct complexes found to be irreversible processes and reaction processes of oxygen for oxygen adduct complexes are quasi-reversible process, the potential range was $E_{pc}=-0.85{\sim}-1.19V\;and\;E_{pa}=-0.74{\sim}-0.89V$.

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Factors Influencing Frequency of Abnormal Peak in the Measurement of HbA1c by HPLC (HPLC법을 이용한 HbA1c 측정시 Abnormal Peak의 빈도와 원인)

  • Kim, Sun-Kyung;Bae, Ae-Young;Choi, Dae-Yong;Kim, Myung-Soo;Yoo, Kwang-Hyun;Ki, Chang-Seok
    • Korean Journal of Clinical Laboratory Science
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    • v.37 no.2
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    • pp.71-77
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    • 2005
  • We experienced the specimen that contains a hemoglobin variant known as interference from HbAS in October 2003. It was the first case of Hb variants since Samsung Medical Center began conducting glycohemoglobin College of American Pathologists surveys in 1997. The purpose of this study is to share our experience with the specimen and promote the understanding of Hb variants & derivatives. We've performed cross checks to examine HbA1c by using two pieces of equipment; the TOSHOH G7 and BIO-RAD VARIANT-T(turbo), and Automatic High Performance Liquid Chromatography(HPLC) as an analytic measurement method. HPLC provides different fractional information of hemoglobin with a two-dimensional graph as well as numeric results. We have been performing a "Systematic Checking Process". Three specimen suspicious of Hb variants & derivatives were found through this process. College of American Pathologists notified that it is important for users to be aware of the limitation of their glycohemoglobin method to avoid reporting incorrect results due to interference from hemoglobin variants or hemoglobin adducts. Therefore, laboratory findings of Hb variants & derivatives are very important. The experience of qualified technicians with professional knowledge in Hb variants is the most important aspect in finding Hb variants. Korea is homogeneous in race and is not in an area with a higher finding rate of Hb variants. While 1,024 cases of Hb variants have been found in Japan, we do not have specific data on how many cases of Hb variants have been found in Korea. Considering Hb variant cases in Japan, which is geographically close to us, it is presumed that there must be various Hb variant cases in Korea. If domestic laboratories set a systemic protocol and build a network to share our experience in Hb variants, I expect the Korean Hb variants could also be listed on the world's Hb variant list.

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Tobacco Use Increases Oxidative DNA Damage in Sperm - Possible Etiology of Childhood Cancer

  • Kumar, Shiv Basant;Chawla, Bhavna;Bisht, Shilpa;Yadav, Raj Kumar;Dada, Rima
    • Asian Pacific Journal of Cancer Prevention
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    • v.16 no.16
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    • pp.6967-6972
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    • 2015
  • Background: Cigarette smoking and tobacco chewing are common modes of consuming tobacco all over the world. Parents need to be aware that germ cell integrity is vital for birth of healthy offspring as biological parenting begins much before birth of a child and even before conception. The present study was conducted to determine the etiology of non-familial sporadic heritable retinoblastoma (NFSHRb), by evaluating oxidative sperm DNA damage in fathers due to use of tobacco (smoking and chewing). Materials and Methods: We recruited 145 fathers of NFSHRb children and 53 fathers of healthy children (controls) in the study. Tobacco history was obtained by personal interview. Seminal reactive oxygen species (ROS) in semen, sperm DNA fragmentation index (DFI) and 8 hydroxy 2' deoxyguanosine (8-OHdG) levels in sperm were evaluated. The RB1 gene was screened in genomic blood DNA of parents of children with NFSHRb and controls. Odds ratios (ORs) derived from conditional logistic regression models. Results: There was significant difference in the levels of ROS (p<0.05), DFI (p<0.05) and 8-OHdG (p<0.05) between tobacco users and non-users. The OR of NFSHRb for smokers was 7.29 (95%CI 2.9-34.5, p<0.01), for tobacco chewers 4.75 (2.07-10.9, p<0.05) and for both 9.11 (3.79-39.2; p<0.01). Conclusions: This study emphasizes the adverse effect of tobacco on the paternal genome and how accumulation of oxidative damage in sperm DNA may contribute to the etiology of NFSHRb. In an ongoing parallel study in our laboratory, 11 of fathers who smoked underwent. Meditation and yoga interventions, showed significant decline in levels of highly mutagenic oxidised DNA adducts after 6 months. Thus our lifestyle and social habits impact sperm DNA integrity and simple interventions like yoga and meditation are therapeutic for oxidative damage to sperm DNA.

Gene Expression Profiling in Diethylnitrosamine Treated Mouse Liver: From Pathological Data to Microarray Analysis (Diethylnitrosamine 처리 후 병리학적 결과를 기초로 한 마우스 간에서의 유전자 발현 분석)

  • Kim, Ji-Young;Yoon, Seok-Joo;Park, Han-Jin;Kim, Yong-Bum;Cho, Jae-Woo;Koh, Woo-Suk;Lee, Michael
    • Toxicological Research
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    • v.23 no.1
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    • pp.55-63
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    • 2007
  • Diethylnitrosamine (DEN) is a nitrosamine compound that can induce a variety of liver lesions including hepatic carcinoma, forming DNA-carcinogen adducts. In the present study, microarray analyses were performed with Affymetrix Murine Genome 430A Array in order to identify the gene-expression profiles for DEN and to provide valuable information for the evaluation of potential hepatotoxicity. C57BL/6NCrj mice were orally administered once with DEN at doses of 0, 3, 7 and 20 mg/kg. Liver from each animal was removed 2, 4, 8 and 24 hrs after the administration. The histopathological analysis and serum biochemical analysis showed no significant difference in DEN-treated groups compared to control group. Conversely, the principal component analysis (PCA) profiles demonstrated that a specific normal gene expression profile in control groups differed clearly from the expression profiles of DEN-treated groups. Within groups, a little variance was found between individuals. Student's t-test on the results obtained from triplicate hybridizations was performed to identify those genes with statistically significant changes in the expression. Statistical analysis revealed that 11 genes were significantly downregulated and 28 genes were upregulated in all three animals after 2 h treatment at 20 mg/kg. The upregulated group included genes encoding Gdf15, JunD1, and Mdm2, while the genes including Sox6, Shmt2, and SIc6a6 were largely down regulated. Hierarchical clustering of gene expression also allowed the identification of functionally related clusters that encode proteins related to metabolism, and MAPK signaling pathway. Taken together, this study suggests that match with a toxicant signature can assign a putative mechanism of action to the test compound if is established a database containing response patterns to various toxic compounds.

THE EFFECT OF GENETIC VARIATION IN THE DNA BASE REPAIR GENES ON THE RISK OF HEAD AND NECK CANCER (DNA 염기손상 치유유전자의 변이와 두경부암 발생 위험성)

  • Oh, Jung-Hwan;Yoon, Byung-Wook;Choi, Byung-Jun
    • Journal of the Korean Association of Oral and Maxillofacial Surgeons
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    • v.34 no.5
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    • pp.509-517
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    • 2008
  • DNA damage accumulates in cells as a result of exposure to exogenous agents such as benzopyrene, cigarette smoke, ultraviolet light, X-ray, and endogenous chemicals including reactive oxygen species produced from normal metabolic byproducts. DNA damage can also occur during aberrant DNA processing reactions such as DNA replication, recombination, and repair. The major of DNA damage affects the primary structure of the double helix; that is, the bases are chemically modified. These modification can disrupt the molecules'regular helical structure by introducing non-native chemical bonds or bulky adducts that do not fit in the standard double helix. DNA repair genes and proteins scan the global genome to detect and remove DNA damage and damage to single nucleotides. Direct reversal of DNA damage, base excision repair, double strand break. DNA repair are known relevant DNA repair mechanisms. Four different mechanisms are distinguished within excision repair: direct reversal, base excision repair, nucleotide excision repair, and mismatch repair. Genetic variation in DNA repair genes can modulate DNA repair capacity and alter cancer risk. The instability of a cell to properly regulate its proliferation in the presence of DNA damage increase risk of gene mutation and carcinogenesis. This article aimed to review mechanism of excision repair and to understand the relationship between genetic variation of excision repair genes and head and neck cancer.

Antigenotoxicity of Ginseng Petroleum Ether Extract and its Action Mechanism (인삼 지용성성분인 유전독성억제효과와 작용기전)

  • 허문영
    • Journal of Food Hygiene and Safety
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    • v.13 no.3
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    • pp.243-251
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    • 1998
  • Panax ginseng C.A. Meyer has been extensively used in the traditional oriental medicine as a restorative, tonic and prophylatic agent. Petroleum ether extract of panax ginseng C.A. Meyer (GPE) and its several fractions (PI-P5) were tested for the evaluation of antigenotoxicity against N-methyl-N-nitrosourea (MNU) and benzo(a)pyrene [B(a)P]-induced micronucleated reticulocytes in mouse peripheral blood. GPE and P2 showed more significant anticlastogenicity than other fractions did. To elucidate the anticlastogenic action mechanism of GPE and P2 against B(a)P, the alteration of B(a)P metabolism was studied. GPE and P2 inhibited B(a)P metabolism in the presence of 8-9 mix and decreased B(a)P-DNA binding in calf thymus DNA with 8-9 mix. They also decreased [$^3H$] MNU induced DNA binding and methylation to 7-methyl guanine and $O^{6}-methyl$ guanine adducts in calf thymus DNA by RPLC analysis. These results suggest that the anticlastogenicity of GPE and P2 on the B(a)P or MNU-induced clastogenicity is due to decrease of DNA binding with B(a)P or MNU, the inhibition of metabolism with B(a)P and the inhibition of methylation in DNA. Therefore, GPE and P2 may be useful chemopreventive agents of alkylating agent like MNU and secondary carcinogen like B(a)P.

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Affinity for 57Co-Vitamin B12 by a Wide Histologic Variety of Tumor Types in Mice (생쥐 종양모델에서 57Co-Vitamin B12의 종양 친화성에 관한 연구)

  • Sohn, Myung-Hee;Park, Soon-A;Kim, Su-Hyun;Chung, Gyung-Ho;Yim, Chang-Yeol
    • The Korean Journal of Nuclear Medicine
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    • v.32 no.1
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    • pp.89-98
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    • 1998
  • The search for tumor-avid agents for use in nuclear medicine imaging is an ongoing field of importance. The purpose of this study was to determine the affinity for radio labeled vitamin $B_{12}$ by a wide histologic variety of tumor types in mice. Seventeen different types of tumor were grown subcutaneously in female Balb/C or Balb nu/nu(nude) mice. When the tumors reached about 1 cm in diameter, mice were injected intraperitoneally with $^{57}Co$-vitamin $B_{12}$. Twenty-four hours later, the mice were sacrificed. Organs and tissues were removed, weighed, and activity per mg determined by gamma counter. Values represented cpm/mg tissue that was normalized to 20 grams body weight for each mouse. A wide variety of tumor types showed significant uptake and concentration of $^{57}Co$-vitamin $B_{12}$, as evidenced by tumor:tissue activity ratios. For many tissues of great importance in terms of background(bone, muscle, blood), the tumor:tissue activity ratios of uptake were high. These data strongly suggest that further efforts to evaluate the utility of radio labeled adducts of vitamin $B_{12}$ for clinical use in oncologic imaging are warranted.

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Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.919-925
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    • 2011
  • A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UV-VIS, $^1H$- and $^{13}C$- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in $CD_3OD+10%D_2O$ after exposure to $^{60}Co-{\gamma}$-rays at 77 K using a 0.2217 M rad $h^{-1}$ vicrad source showed $g_{\perp}$ > $g_{\parallel}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_z2$ orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with ${\gamma}$-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the $dz^2$ orbital occurs. However, the ESR spectrum in solid state after exposure to $^{60}Co-{\gamma}$-rays at 77 K showed $g_{\parallel}$ > $g_{\perp}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_x2_{-y}2$ ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, $[H_{12}LMn]Cl_4.2H_2O$, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, $[H_{12}LFe]Cl_5.H_2O$, showed spectrum of a high spin $^{57}Fe$ (I=1/2), $d^5$ configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.