• Title/Summary/Keyword: Bulky binding

Search Result 15, Processing Time 0.031 seconds

Mass spectrometric studies of competitive binding of C60 and C70 to mesosubstituted porphyrins

  • Jung, Sung-Han;Shin, Seung-Koo
    • Mass Spectrometry Letters
    • /
    • v.2 no.2
    • /
    • pp.49-52
    • /
    • 2011
  • Competitive binding of $C_{60}$ and $C_{70}$ to meso-substituted porphyrins was studied by mass spectrometry (MS). Electrospray ionization MS was employed to acquire the mass spectra of 1 : 1 porphyrin-fullerene complexes formed in a mixture of mesosubstituted porphyrin and fullerite to determine the ratio of complexes between $C_{60}$ and $C_{70}$. Matrix-free laser desorption ionization MS was used to obtain the mass spectra of fullerite to measure the mole fraction of $C_{60}$ and $C_{70}$. The binding constant ratio ($K_{70}$/$K_{60}$) was determined from the mass spectral data. The difference in standard Gibbs free energy change, ${\Delta}({\Delta}G^o)_{70-60}$, for the competitive binding of $C_{60}$ and $C_{70}$ was calculated from $K_{70}$/$K_{60}$. Of the five porphyrins, tetraphenyl, tetra(4-pyridyl), tetra(4-carboxyphenyl), tetra(3,5-di-tert-butylphenyl), and tetra(pentafluorophenyl) porphyrins, the first three non-bulky porphyrins yield negative values of ${\Delta}({\Delta}G^o)_{70-60}$, whereas the other two bulky porphyrins result in positive values of ${\Delta}({\Delta}G^o)_{70-60}$. This result indicates that $C_{70}$ binding to porphyrin is thermodynamically favored over $C_{60}$ binding in non-bulky porphyrins, but disfavored in bulky ones. It also suggests that the binding mode of $C_{70}$is different between non-bulky and bulky porphyrins, which is in line with previous experimental findings of the "side-on" binding to non-bulky porphyrins and the $C_{60}$-like "end-on" binding to bulky porphyrins.

Cobalt(III) Complexes of Various Salen-Type Ligand Bearing Four Quaternary Ammonium Salts and Their Reactivity for CO2/Epoxide Copolymerization

  • Kim, Bo-Eun;Varghese, Jobi Kodiyan;Han, Yong-Gyu;Lee, Bun-Yeoul
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.4
    • /
    • pp.829-834
    • /
    • 2010
  • Ligand variation was carried out on a cobalt(III) complex of Salen-type ligand comprised of 1,2-cyclohexenediamine and salicylaldehyde bearing a methyl substituent on 3-position and -[$CMe(CH_2CH_2CH_2N^+Bu_3)_2$] on 5-position, which is a highly active catalyst for $CO_2$/propylene oxide copolymerization. Replacement of the methyl substituent with bulky isopropyl group resulted in alteration of the binding mode, consequently lowering turnover frequency significantly. Replacement with an ethyl group preserved binding mode and activity. Replacement of the tributylammonium unit with trihexylammonium or trioctylammonium, or replacement of 1,2-cyclohexenediamino unit with -$NC(Me)_2CH_2N$- decreased activity, even though the binding mode was unaltered.

DNA Binding Mode of the Isoquinoline Alkaloid Berberine with the Deoxyoligonucleotide d(GCCGTCGTTTTACA)2

  • Park, Hye-Seo;Kim, Eun-Hee;Sung, Yoon-Hui;Kang, Mi-Ran;Chung, In-Kwon;Cheong, Chae-Joon;Lee, Weon-Tae
    • Bulletin of the Korean Chemical Society
    • /
    • v.25 no.4
    • /
    • pp.539-544
    • /
    • 2004
  • The ability of protoberberine alkaloids, berberine and berberrubine, to act as topoisomerase II poisons is linked to the anti-cancer activity. Minor alterations in structure have a significant effect on their relative activity. Berberine, which has methoxy group at the 19-position, is significantly less potent than berberrubine. Several observations support non-specific binding to HP14 by the berberine: (i) nonspecific upfield changes in $^1H$ chemical shift for protons of the berberine; (ii) the broadening of imino protons of HP14 upon binding of the berberine; (iii) very small increases in duplex melting temperature in the presence of the berberine. Our results reveal that substitution of a hydroxyl group to a methoxy group on the 19-position, thereby converting the berberrubine to the berberine is associated with a non-specific DNA binding affinity and a reduced topoisomerase II poisoning. The presence of a bulky 19-methoxy substituent decreases intercalating properties of berberine and makes it inactive as topoisomerase II poison.

Recognition of DNA Damage in Mammals

  • Lee, Suk-Hee
    • BMB Reports
    • /
    • v.34 no.6
    • /
    • pp.489-495
    • /
    • 2001
  • DNA damage by UV and environmental agents are the major cause of genomic instability that needs to be repaired, otherwise it give rise to cancer. Accordingly, mammalian cells operate several DNA repair pathways that are not only responsible for identifying various types of DNA damage but also involved in removing DNA damage. In mammals, nucleotide excision repair (NER) machinery is responsible for most, if not all, of the bulky adducts caused by UV and chemical agents. Although most of the proteins involved in NER pathway have been identified, only recently have we begun to gain some insight into the mechanism by which proteins recognize damaged DNA. Binding of Xeroderma pigmentosum group C protein (XPC)-hHR23B complex to damaged DNA is the initial damage recognition step in NER, which leads to the recruitment of XPA and RPA to form a damage recognition complex. Formation of damage recognition complex not only stabilizes low affinity binding of XPA to the damaged DNA, but also induces structural distortion, both of which are likely necessary for the recruitment of TFIIH and two structure-specific endonucleases for dual incision.

  • PDF

Conservation of Minutes of the Cabinet Meeting held by the National Archives of Korea Measures to Improve the Binding Methods for Bulky Bound Records (국가기록원 소장 국무회의록 보존처리 -거대 편철 기록물의 보존성 향상을 위한 편철 개선-)

  • Lee, Hyunjin;Jeong, Seongeun;Jo, Dayoung;Choi, Bora;Ko, Soorin;Kim, Taehwi;Cho, Eunhye
    • Conservation Science in Museum
    • /
    • v.22
    • /
    • pp.27-40
    • /
    • 2019
  • Minutes of cabinet meetings (hereafter referred to as "minutes") offer records on important activities of the government of the Republic of Korea. The National Archives of Korea has implemented a series of preservation for these minutes such as condition survey, deacidification, microfilming, digitization, making boxes, etc. Conservation treatment plans were further established in 2018 to pursue more preservation of over 2,000 volumes of minutes based on the result of the condition survey of the minutes. Among ninety-seven volumes that require conservation treatments, six volumes have been treated so far. A major concern of conservation treatment of minutes was found that a single volume of minutes contains 800 pages, leading to heavier and bulkier than most of other bound volumes. This paper presents the measures taken to solve the problems resulting from this bulky structure of the bound minutes. It is expected that the study will offer an opportunity to consider effective conservation methods for records on paper of which the physical shapes are yet to be determined.

Conjugates of Enkephalin Analogs: Synthesis and Discrimination of μ and δ Opioid Receptors Based on Membrane Compartment Concept

  • Hong, Nam-Joo;Jin, Dong-Hoon;Hong, Eun-Young
    • Bulletin of the Korean Chemical Society
    • /
    • v.30 no.3
    • /
    • pp.599-607
    • /
    • 2009
  • A series of conjugated cyclic and linear enkephalin analogs, Tyr-c[D-A2bu-Gly-Phe-Asp(NH-X)], where X = methyl, stearyl or$ PEG_350$, and Tyr-D-Ala-Gly-Phe-Cys(S-X), where X = methyl, octyl, or farnesyl, were synthesized in solution to investigate the receptor selectivity of opioids based on Schwyzer's membrane compartment $concepts.^{5,6}$ Cyclizations of the target compounds were achieved in high yields (> 60%) employing BOP, $NaHCO_3$ in DMF despite the steric hindrance of the bulky pendant groups. In the binding assay, the hydrophobic fatty acyl conjugates retained $\mu$-receptor selectivity. The unsaturated farnesyl conjugate exhibited the increased binding affinity than the saturated stearyl conjugate for both $\mu$-and $\delta$-opioid receptors. The PEG conjugates displayed the $\delta$-receptor selectivity. The low molecular weight $PEG_350$ conjugate exhibited the increase selectivity than the high molecular weight $PEG_5000$ conjugate to the $\delta$-receptor. The results of this study support the membrane compartment concepts.

Synthesis and Characterization of Dichloro and Dibromo(2-(dimethylaminomethyl)thiophene) Copper(II) Complexes

  • Kim, Young-Inn;Choi, Sung-Nak;Ro, Chul-Un
    • Bulletin of the Korean Chemical Society
    • /
    • v.15 no.7
    • /
    • pp.549-553
    • /
    • 1994
  • The 2-(dimethylaminomethyl)thiophene (dmamt) complexes with copper(II) chloride and bromide were prepared and characterized by optical, EPR, XPS spectroscopies and magnetic susceptibility measurements. The low-energy absorption band above 850 nm and the relatively small EPR hyperfine coupling constant ($A_{//}{\simeq}$125 G) indicate the pseudotetrahedral site symmetry around copper(II) ion both in Cu(dmamt)$Cl_2$ and Cu(dmamt)$Br_2$ complexes. The higher satellite to main peak intensity of Cu $2P_{3/2}$ core electron binding energy in XPS spectra also supports the pseudotetrahedral geometry around the copper(II) ions having $CuNSX_2$ chromophores. The distortion from square-planar to pseudotetrahedral symmetry is likely to arise from the steric hindrance of the bulky dmamt ligand in the complex. Magnetic susceptibility study shows that these compounds follow Curie-Weiss law in the temperature range of 77-300 K with positive Weiss constant exhibiting the ferromagnetic interaction between copper(II) ions in solid state.

A Disposable Grating-Integrated Multi-channel SPR Sensor Chip for Detection of Biomolecule (회절격자가 집적된 일회용 다중채널 SPR 생체분자 검출 칩)

  • Jin, Young-Hyun;Cho, Young-Ho
    • The Transactions of The Korean Institute of Electrical Engineers
    • /
    • v.58 no.1
    • /
    • pp.147-154
    • /
    • 2009
  • This paper presents a grating~integrated SPR (Surface Plasmon Resonance) sensor chip for simple and inexpensive biomolecule detection. The grating-integrated SPR sensor chip has two sensing channels having a nano grating for SPR coupling. An external mirror is used for multi channel SPR sensing. The present sensor chip replaces bulky and expensive optical components, such as fiber-optic switches or special shaped prisms, resulting in a simple and inexpensive wavelength modulated multi-channel SPR sensing system. We fabricate a SPR sensor chip integrated with 835 nm-pitch gratings by a micromolding technique to reduce the fabrication cost. In the experimental characterization, the refractive index sensitivity of each sensing channel is measured as $321.8{\pm}8.1nm$/RI and $514.3{\pm}8.lnm$/RI, respectively. 0.5uM of the target biomolecule (streptavidin) was detected by a $1.13{\pm}0.16nm$ shift of the SPR dip in the 10%-biotinylated sample channel, while the SPR dip in the reference channel for environmental perturbation monitoring remained at the same position. From the experimental results, multi-channel biomolecule detection capability of the present grating-integrated SPR sensor chip has been verified. On the basis of the preliminary experiments, we successfully measured the binding reaction rate for the $2\;nM{\sim}200\;nM$ monoclonal-antibiotin, thus verifying biomolecule concentration detectability of the present SPR sensor chip. The binding reaction rates measured from the present SPR sensor chip agredd well with those from a commercialized SPR sensor.

Current Understanding of the Roles of CD1a-Restricted T Cells in the Immune System

  • Yoo, Hyun Jung;Kim, Na Young;Kim, Ji Hyung
    • Molecules and Cells
    • /
    • v.44 no.5
    • /
    • pp.310-317
    • /
    • 2021
  • Cluster of differentiation 1 (CD1) is a family of cell-surface glycoproteins that present lipid antigens to T cells. Humans have five CD1 isoforms. CD1a is distinguished by the small volume of its antigen-binding groove and its stunted A' pocket, its high and exclusive expression on Langerhans cells, and its localization in the early endosomal and recycling intracellular trafficking compartments. Its ligands originate from self or foreign sources. There are three modes by which the T-cell receptors of CD1a-restricted T cells interact with the CD1a:lipid complex: they bind to both the CD1a surface and the antigen or to only CD1a itself, which activates the T cell, or they are unable to bind because of bulky motifs protruding from the antigen-binding groove, which might inhibit autoreactive T-cell activation. Recently, several studies have shown that by producing TH2 or TH17 cytokines, CD1a-restricted T cells contribute to inflammatory skin disorders, including atopic dermatitis, psoriasis, allergic contact dermatitis, and wasp/bee venom allergy. They may also participate in other diseases, including pulmonary disorders and cancer, because CD1a-expressing dendritic cells are also located in non-skin tissues. In this mini-review, we discuss the current knowledge regarding the biology of CD1a-reactive T cells and their potential roles in disease.

How Do Oroxylin A and Spinosin Exert Their Activities on Cognitive Function?

  • Bae, Ho Jung;Park, Ho Jae;Kim, Dong Hyun;Ryu, Jong Hoon
    • Natural Product Sciences
    • /
    • v.26 no.1
    • /
    • pp.1-9
    • /
    • 2020
  • Flavonoids are mainly contained in the vegetables and medicinal herbs. Until now, over 5,000 kinds of flavonoid have been identified and their biological activities have been reported. Among them, we are interested in oroxylin A and spinosin because of their specific structures having bulky group at C-6 of ring A. Oroxylin A is contained in the Scutellaria baicalensis and exhibits cognitive enhancing activity as a GABAA receptor antagonist, which is different from those of mainly contained in the S. baicalenis, baicalein or wogonin. Spinosin is isolated from Zizyphus jujuba var. spinosa and mainly studied as a hypnotic or anxiolytic agent because of traditional knowledge about its original herb. As far as we know, the cognitive function of spinosin was first identified by our group. In this review, we discuss how such flavonoids exert their pharmacological activities associated with cognitive function based on the receptor binding study and behavioral studies. Traditional knowledge and reverse pharmacology may be addressed in the research field of phytochemical pharmacology and useful to unveil the secret of phytochemicals.