• Title/Summary/Keyword: Derivative spectra

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Difference in Susceptibility of Tyrosine Residue to Oxidative Iodination between a Thioredoxin Box Region and a Hormonogenic Region

  • Sok, Dai-Eun;Charles J.Sih
    • Archives of Pharmacal Research
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    • v.24 no.5
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    • pp.446-454
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    • 2001
  • Peptide fragments, isolated from proteolytic cleavage of thyroglobulin at specific sites, were examined for the iodination of tyrosine residues. The 50 kDa polypeptide, which was prepared from digestion of bovine thyroglobulin and continuous preparative SDS-PAGE, was subjected to reduction with DTT and alkylation with iodoacetic acid to generate S-car-boxymethylated peptide derivative, which was further hydrohysed by endoproteinase-Asp-N. Peptide products were separated by RP-HPLC, and each fraction was analyzed by LC/ESI-MS and MALDI-MS analyses. Based on the specificity of endoproteinase-Asp-N andthe mass spectra data, a peptide fragment turned out to correspond to a peptide, DALCCVKCPEGSYFQ (1438-1452), characterized by the presence of a thioredoxin box (CVKC) and a tyrosine residue. In addition, another peptide fragment (1453-1465) containing a thioredoxin box (CIPC) and a tyrosine residue was also observed. However, any evidence of iodination of the tyrosine residue present in these peptides was not provided. Meanwhile, tyrosine residues in the peptides, DVEEALAGKYLAGRFA (1366-1381) and DYSGLLLAFQVFLL (1290-1303) were found to be iodinated; mono- or diiodinated tyrosine residues, characteristic of a hormogenic site, existed in both peptides. In addition, the tyrosine residue in the peptide (1218-1252), corresponding to a hormonogenic site was also iodinated. Thus, there was a sharp difference of the susceptibility to oxidative iodination between the tyrosine residue in a hormonogenic site and that in a thioredoxin region. From these results, it is suggested that polypeptide region adjacent to tyrosine residues may govern the susceptibility of tyrosine to oxidative iodination.

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Regulation of Chlorophyll-Protein Complex Formation and Assembly in Wheat Thylakoid Membrane

  • Guseinova, I.M.;Suleimanov, S.Y.;Aliev, J.A.
    • BMB Reports
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    • v.34 no.6
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    • pp.496-501
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    • 2001
  • Lincomycin, an inhibitor of plastid protein synthesis, was found to block the synthesis of apoprotein P700 with a molecular mass of 72 kDa and the assembly of the Chl a-protein of PS I. Synthesis of the polypeptides of 48, 43.5, and 32 kDa of the PS II complex is also suppressed. This process is accompanied by the disappearance of the PS Two reaction center Chl a at 683 nm, and of the PS One reaction center Chl a at 690, 696, and 705 nm on the fourth derivative of the absorption spectra at 77K. Lincomycin does not affect the synthesis of LHC subunits. It increases the content of the two main Chl forms of LHC at 648 nm (Chl b) and 676 nm (Chl a). The low-temperature fluorescence ratio F736/F685 is also increased. However, the effect of cycloheximide (an inhibitor of cytoplasmic protein synthesis) leads to the reduction of polypeptides of the light-harvesting Chl a/b-protein complex in the range of 29.5-22 kDa. Under these conditions, the relative amount of Chl b and the F736/ F685 fluorescence ratio decrease significantly. This is obviously the result of blocking the LHC I and LHC II synthesis. At the same time rifampicin and actinomycin D (inhibitors which block transcription in chloroplast and nuclear genome, respectively) inessentially affect the characteristics of these complexes.

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Characterization of Quorum-Sensing Signaling Molecules Produced by Burkholderia cepacia G4

  • Park, Jun-Ho;Hwang, In-Gyu;Kim, Jin-Wan;Lee, Soo-O;Conway, B.;Peter Greenberg, E.;Lee, Kyoung
    • Journal of Microbiology and Biotechnology
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    • v.11 no.5
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    • pp.804-811
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    • 2001
  • In many Gram-negative bacteria, autoinducers, such as N-acyl-L-homoserine lactone(acyl-HSL) and its derivative molecules, mediate the cell-density-dependnet expression of certain operons. The current study identified the autoinducers produced by Burkholderia cepacia G4, a trichloroethylene-degrading lagoon isolate, using TLC bioassays with Agrobacterium tumefaciens NT1(pDCI141E33) and Chromobacterium violaceum CVO26, and a GC-MS analysis. The ${R_f}\;and\;{R_t}$ values and mass spectra were compared with those of synthetic compounds. Based on the analyses, it was confirmed that G4 produces N-hexanoyl (C6)-, N-octanoyl (C8)-, N-decanoyl (C10)-, N-dodecanoyl (C12)-HSL, and an unknown active species. The integration of the GC peak areas exhibited a ratio of C8-HSL:C10-HSL:C12-HSL at 3:17:1 with C6-HSL and C10-HSL production at trace and micromolar levels, respectively, in the culture supernatants. Nutants partially defective in producing acyl-HSLs were also partially defective in the biosynthesis of an antibiotic substance. These results indicate that the autoinducer-dependent gene regulation in G4 is dissimilar to the clinical B. cepacia strains isolated from patients with cystic fibrosis.

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Identification of Pharmaceuticals for process control using Near Infrared Spectroscopy and Soft Independence modeling of Class Analogy (SIMCA)

  • Cho, Chang-Hee;Kim, Hyo-Jin;Maeng, Dae-Young;Seo, Sang-Hun;Cho, Jung-Hwan
    • Near Infrared Analysis
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    • v.1 no.2
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    • pp.29-33
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    • 2000
  • The identification step of raw drug materials is an indispensible procedure in the GMP manufacturing process within the pharmaceutical industry. However, wet chemistry methods for identification of drug materials, used by the various Pharmacopeia are time-consuming and expensive steps. In this paper, near-infrared spectroscopy (NIRS) has been developed for identifying eleven drug substances including calcium pantothenate, cefaclor, cefoperazone, cephradine, dextromethorphan, ehtambutol, nicotinamide, pyrozinamide, tramadol, vitamin C, and vitamin E. Also the aim of ths work is to consturct a new algorithm for calibration model using soft independence modeling of class analogy (SIMCA) with Malinowskis Indicator Function (IND), which is used for finding the number of principal components of each class of the SIMACA model. The use of NIR technique with pattern recognition to qualify raw materials can make it possible to monitor process in real time as well as to control all procedures in the pharmaceutical industry. As the result, the samples identified of 183 different batches from 11 different compounds were separated clearly by SIMCA with 2nd derivative spectra in the NIR region of 1100∼2400 nm.

A Novel Bromoindole Alkaloid from a Korean Colonial Tunicate Didemnum sp.

  • Hahn, Dongyup;Kim, Geum Jin;Choi, Hyukjae;Kang, Heonjoong
    • Natural Product Sciences
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    • v.21 no.4
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    • pp.278-281
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    • 2015
  • Chemical investigation on a colonial marine tunicate, Didemnum sp. led to the isolation of a series of indole alkaloids including a new (1) and two known metabolites (2-3). Based on the spectroscopic analysis including 1D and 2D NMR along with MS spectra, the structure of 1 (16-epi-18-acetyl herdmanine D) was elucidated as a new amino acid derivative. The absolute configuration of 1 was determined by comparison of specific rotation with the known compound. The structures of compounds 2 and 3 were also identified as bromoindole containing compounds N-(6-bromo-1H-indole-3-carbonyl)-L-arginine and (6-bromo-^1H-indol-3-yl) oxoacetamide, respectively, based on $^1H$ and $^{13}C$ NMR data, MS data and specific rotation value. Their pharmacological potentials as antibacterial agents and FXR antagonists were investigated, but no significant activity was found. However, the structural similarity of compound 1 to compound 4 suggested the anti-inflammatory potential of compound 1.

Producibility of Aflatoxins by Aspergillus flavus Group Isolated from Deteriolated Rice in Korea (국내(國內)의 변질미(變質米)에서 분리된 Aspergillus flavus 군(群)의 Aflatoxin 생성능(生成能))

  • Lee, Kwan-Young;Lee, Su-Rae
    • Korean Journal of Food Science and Technology
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    • v.6 no.3
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    • pp.169-176
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    • 1974
  • In order to investigate the producibility of aflatoxins by seven Aspergillus flavus strains isolated from deteriolated rice in Korea, polished rice was artificially inoculated and subjected to isolation and quantitation of the mycotoxin. It was proved that all strains were capable of producing aflatoxins, preferentially $B_1$ but no $G_1$ at all and their producibility was closely related to the color of culture media and chloroform extracts. The strain producing the most aflatoxin was A. flavus var. columnaris, excreting 1 ppm on rice. Aflatoxin $B_1$ was isolated and identified by thin-layer chromatography, ultraviolet absorption spectra and derivative formation of water and acetate adducts.

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Inactivation of Brain Succinic Semialdehyde Reductase by o-Phthalaldehyde

  • Song, M.S.;Lee, B.R.;Jang, S.H.;Cho, S.W.;Park, S.Y.
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1995.04a
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    • pp.75-75
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    • 1995
  • Succinic semialdehyde reductase, one of key enzyme of GABA shunt in CNS, is inactivated by o-phthalaldehyde, The inactivation followed pseudo first-order kinetics, and the second-order rate constant for the inactivation process was 28 M$\^$-1/s$\^$-1/ at pH 7.4 and 25$^{\circ}C$. The absorption spectrum(λ$\_$max/=377nm), fluorescence exitation(λ$\_$max/=340nm) and fluorescence emission spectra (λ$\_$max/=409nm) were consistent with the formation of an isoindole derivative in the catalytic site between a cysteine and a lysine residues about 3${\AA}$ apart. The substrate, succinic semialdehyde, did not protect the enzymatic activity against inactivation, whereas the coenzyme, NADPH, protected against o-phthalaldehyde induced inactivation of the enzyme. About 1 isoindole group per moi of the enzyme was formed following complete loss of the enzymatic activity. These results suggest that the amino acid residues of the enzyme participating in reaction with o-phthalaldehyde more likely residues at or near the coenzyme binding site.

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SYNTHETIC DEVELOPMENT OF NEW 1$\beta$-SUBSTITUTED CARBAPENEMS

  • Nagao, Yoshimitsu
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1993.04a
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    • pp.34-35
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    • 1993
  • The Development of new asymmetric induction methods useful for syntheses of biologically active natural products and drugs, using C4-chiral 1,3-th-iazolidine-2-thiones, has been a recent focus of interest. 1-8) The present account describes the significance of particular heterocycles in the synthetic development of new 1${\beta}$-substituted carbapenems. A fungal metabolite, (+)-thienamycin (1) has attracted one's attention as a hopeful candidate for new-generation antibiotic drugs because of its strong antimicrobial activities and wide antimicrobial spectra due to the extensive inhibition against various ${\beta}$-lactamases. However, it has been serious problems toward a practically useful drug that (+)-thienamycin is fairly labile in the solution and can be metabolized by renal dehydropept- idase-I (DHP-I). Recently, a Merck Sharp & Dohme research group exploited a non-natural ${\beta}$-lactam, imipenem (2) which has been appeared in the drug market as the first carbapenem-type antibiotic drug. 9) However 2 must be used with a DHP-I inhibitor, cilastatin sodium (3).9) Thus, a 1,${\beta}$-methyl- carbapenem derivative 4 has been disclosed by the same group. 10) It seems to be more hopeful candidate as a new-generation antibiotic because it can directly resist against metabolism by the renal DHP-1 without an enzyme inhibitor 3. 10)

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Micro-Chemical Structure of Polyaniline Synthesized by Self-Stabilized Dispersion Polymerization

  • NamGoong, Hyun;Woo, Dong-Jin;Lee, Suck-Hyun
    • Macromolecular Research
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    • v.15 no.7
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    • pp.633-639
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    • 2007
  • A variety of NMR techniques were applied to the micro-chemical structural characterization of polyanilines prepared via an efficient synthetic method in a self-stabilized dispersion medium in which the polymerization was conducted in a heterogeneous organic/aqueous biphasic system without any stabilizers. Here, the monomer and growing polymer chain were shown to function simultaneously as a stabilizer, imparting compatibility for the dispersion of the organic phase, and as a form of flexible template in an aqueous reaction medium. Polymerizations predicated on this concept generated polyanilines with a low defect content: solution state $^{13}C-NMR$ and solid $^{13}CDD/CP/MAS$ spectroscopy indicated that the synthesized HCPANi and its soluble derivative, HCPANi-t-BOC, evidenced distinctly different NMR spectra with fewer side peaks, as compared to conventionally prepared PANis, and the complete structural assignments of the observed NMR peaks could be determined via the combination of both 1D and 2D techniques. Ortho-linked defects in HCPANi were estimated to be as low as 7%, as shown by a comparison of the integration of the carbonyl carbon resonance peaks.

Photophysical and Electrochmical Studies of N,N-Bis (2,5-di-tert-butylphenyl) - 3,4,9,10 perylenebis (dicarboximide) (DBPI)

  • El-Hallag, Ibrahim S.;El-Daly, Samy A.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.989-998
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    • 2010
  • The titled dye of DBPI gives amplified spontaneous emission (ASE) with maximum at 580 nm upon pumping by nitrogen laser (${\lambda}_{ex}\;=\;337.1\;nm$). The ground state absorption cross section (${\sigma}_A$) and emission cross section (${\sigma}_E$) as well as effective emission cross section(${\sigma}^*_E$) have been determined. The electronic absorption spectra of DBPI were measured in ethanol and tetrahydrofuran at room and low temperature. DBPI displays molecular aggregation in water. The photochemical reactivity of DBPI was also studied in carbon tetrachloride upon irradiation with 525 nm light. The electrochemical investigation of DBPI dye has been carried out using cyclic voltammetry and convolution deconvolution voltammetry combined with digital simulation technique at a platinum electrode in 0.1 mol/L tetrabutyl ammonium perchlorate (TBAP) in two different solvents acetonitrile ($CH_3CN$) and dimethylformamide (DMF). The species were reduced via consumption of two sequential electrons to form radical anion and dianion (EE mechanism). In switching the potential to positive direction, the compound was oxidized by loss of two sequential electrons, which were followed by a fast dimerization and/or aggregation process i.e $EC_{dim1}EC_{dim2}$ mechanism. The electrode reaction pathway and the chemical and electrochemical parameters of the investigated compound were determined using cyclic and convolutive voltammetry. The extracted electrochemical parameters were verified and confirmed via digital simulation method.