• Title/Summary/Keyword: Amine donor

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Exploring the Nucleophilic N- and S-Glycosylation Capacity of Bacillus licheniformis YjiC Enzyme

  • Bashyal, Puspalata;Thapa, Samir Bahadur;Kim, Tae-Su;Pandey, Ramesh Prasad;Sohng, Jae Kyung
    • Journal of Microbiology and Biotechnology
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    • v.30 no.7
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    • pp.1092-1096
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    • 2020
  • YjiC, a glycosyltransferase from Bacillus licheniformis, is a well-known versatile enzyme for glycosylation of diverse substrates. Although a number of O-glycosylated products have been produced using YjiC, no report has been updated for nucleophilic N-, S-, and C- glycosylation. Here, we report the additional functional capacity of YjiC for nucleophilic N- and S- glycosylation using a broad substrate spectrum including UDP-α-D-glucose, UDP-N-acetyl glucosamine, UDP-N-acetylgalactosamine, UDP-α-D-glucuronic acid, TDP-α-L-rhamnose, TDP-α-D-viosamine, and GDP-α-L-fucose as donor and various amine and thiol groups containing natural products as acceptor substrates. The results revealed YjiC as a promiscuous enzyme for conjugating diverse sugars at amine and thiol functional groups of small molecules applicable for generating glycofunctionalized chemical diversity libraries. The glycosylated products were analyzed using HPLC and LC/MS and compared with previous reports.

Donor-π-Acceptor Type Diphenylaminothiophenyl Anthracene-mediated Organic Photosensitizers for Dye-sensitized Solar Cells

  • Heo, Dong Uk;Kim, Sun Jae;Yoo, Beom Jin;Kim, Boeun;Ko, Min Jae;Cho, Min Ju;Choi, Dong Hoon
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1081-1088
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    • 2013
  • Two new metal-free organic dyes bridged by anthracene-mediated ${\pi}$-conjugated moieties were successfully synthesized for use in a dye-sensitized solar cell (DSSC). A N,N-diphenylthiophen-2-amine unit in these dyes acts as an electron donor, while a (E)-2-cyano-3-(thiophen-2-yl)acrylic acid group acts as an electron acceptor and an anchoring group to the $TiO_2$ electrode. The photovoltaic properties of (E)-2-cyano-3-(5-((10-(5-(diphenylamino)thiophen-2-yl)anthracen-9-yl)ethynyl)thiophen-2-yl)acrylic acid (DPATAT) and (E)-2-cyano-3-(5'-((10-(5-(diphenylamino)thiophen-2-yl)anthracen-9-yl)ethynyl)-2,2'-bithiophen-5-yl)acrylic acid (DPATABT) were investigated to identify the effect of conjugation length between electron donor and acceptor on the DSSC performance. By introducing an anthracene moiety into the dye structure, together with a triple bond and thiophene moieties for fine-tuning of molecular configurations and for broadening the absorption spectra, the short-circuit photocurrent densities ($J_{sc}$), and open-circuit photovoltages ($V_{oc}$) of DSSCs were improved. The improvement of $J_{sc}$ in DSSC made of DPATABT might be attributed to much broader absorption spectrum and higher molecular extinction coefficient (${\varepsilon}$) in the visible wavelength range. The DPATABT-based DSSC showed the highest power conversion efficiency (PCE) of 3.34% (${\eta}_{max}$ = 3.70%) under AM 1.5 illumination ($100mWcm^{-2}$) in a photoactive area of $0.41cm^2$, with the $J_{sc}$ of $7.89mAcm^{-2}$, the $V_{oc}$ of 0.59 V, and the fill factor (FF) of 72%. In brief, the solar cell performance with DPATABT was found to be better than that of DPATAT-based DSSC.

Electronic Transitions and Ligand Field Analysis of mer-[N-(2-aminoethyl)-1,2-ethanediamine](glycylglycinato) chromium (III) Perchlorate (mer-[Cr(dien)(glygly)]$CIO_4$ 의 전자전이와 리간드장 해석)

  • Choi, Jong Ha;Hong, Yong Pyo;Park, Yu Chul
    • Journal of the Korean Chemical Society
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    • v.45 no.5
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    • pp.436-441
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    • 2001
  • The emission and excitation spectra of mer-[Cr(dien)(glygly)]ClO$_4$(glygly=glycylglycinate;dien=N-(2-aminoethyl)-1,2-ethanediamine) taken at 77 K are reported. The infrared and visible spectra at 298 K are also measured. The twelve electronic bands due to spin-allowed and spin-forbidden transitions are assigned. Using the observed transitions, a ligand field analysis has been performed to determine the bonding property of coordinated atoms in the chromium(III) complex. It is confirmed that the amine nitrogen atoms of the dien and glygly have strong $\sigma$-donor characters, but the peptide nitrogen of glygly has weak $\pi$-donor property toward chromium(III) ion.

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Optimization of Procedure for Efficient Gene Transfer into Porcine Somatic Cells with Lipofection

  • Kim, D.Y.;McElroy, S.L.
    • Asian-Australasian Journal of Animal Sciences
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    • v.21 no.5
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    • pp.648-656
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    • 2008
  • The objective of this study was to establish conditions for transfection of a foreign gene into somatic cells using cationic lipid reagents and to evaluate the effects of transfection on in vitro development of somatic cell nuclear transfer (SCNT) embryos. Green fluorescent protein (GFP) gene was used as a foreign gene and a non-transfected somatic cell was utilized as a control karyoplast. Monolayers of porcine cells were established and subsequently transfected with a GFP-expressing gene (pEGFP-N1) using three types of transfection reagents (LipofectAMINE PLUS, FuGENE 6 or ExGen500). Donor cells used for SCNT included transfected fetal or adult fibroblasts and oviduct epithelial cells, either serum-fed or serum-starved. Oocytes matured in vitro for 42 h were reconstructed with either transfected or non-transfected porcine somatic cells by electric fusion and activation using a single DC pulse of 1.8 kV/cm for $30{\mu}s$ in $Ca^{2+}$ and $Mg^{2+}-containing$ 0.26 M mannitol solution. Reconstructed oocytes were subsequently cultured in NCSU-23 medium for 168 h and the developmental competence and cell number in blastocyst were compared. There were no significant differences (P>0.05) in fusion, cleavage rates or development to the blastocyst stage between non-transfected, transfected, serum-fed and serum-starved cells. However, the rates of GFP-expressing blastocysts were higher in the FuGENE 6 group (71.4%) among transfection reagents and in the fetal fibroblasts group (70.4%) for donor cells. These results indicate that fetal fibroblasts transfected with FuGENE 6 can be used as donor cells for porcine SCNT and that GFP gene can be safely used as a marker of foreign genes in porcine transgenesis.

The Study of Nitrogen Doner Atoms Chelating Compounds for Removing Heavy Metals (Cd2+,Pb2+,Zn2+,Cu2+) (중금속이몬(Cd2+,Pb2+,Zn2+,Cu2+)제거를 위한 질소를 주개원자로 하는 리간드들의 착화합물 형성에 관한 연구)

  • 김선덕;김준광;김정성
    • Journal of Environmental Science International
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    • v.12 no.4
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    • pp.497-501
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    • 2003
  • The new tridentate ligands of nitrogen donor atoms N,N-Bis(2-amino-ethyI)-benzyl-amine 2HCI(BABEA. 2HCI) and 2,6-Bis(amino-methyl)-pyridien. 2HCI(BAMP. 2HCI) were synthesized as their dihydrochloride salts and characterized by TA, IR. Mass and NMR spectroscopy. The protonation constants of the ligands and stability constants for Cd$^{2+}$, Pb$^{2+}$, Zn$^{2+}$and Cu$^{2+}$ ions were determined by potentiometric titration in aqueous solutions and compared with those of analogous ligands. The effect stability constants of ligands and metal ions for removal of heavy metals in aqueous solution were described.

The Synthetic Potential of SET Photochemistry of Silicon-Substituted Polydonor-Linked Phthalimides

  • Yoon, Ung Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1099-1114
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    • 2006
  • Our studies in the area of single electron transfer (SET) photochemistry have led to the discovery of efficient processes, in which regioselective formation of carbon-centered radicals takes place by nucleophile assisted desilylation of $\alpha$-trialkylsilyl substituted ether, thioether, amine and amide centered cation radicals. The rates of bimolecular desilylation of the intermediate cation radicals exceed those of other cation radical $\alpha$-fragmentation processes (e.g.,-deprotonation). This sereves as the basis for the design of highly regioselective, SET-induced photomacrocyclization reactions of polyether, polythioether, polyamide, and polypeptide linked phthalimides. Photocyclization reactions of trimethylsilyl-terminated substrates in these families are unique in that they produce polyfunctionalized macrocyclic substances in a highly efficient and regioselective manner. In addition, our studies in this area have led to important information about the factors that govern chemical and quantum efficiencies that should be applicable to a wide variety of redox processes promoted by SET from substrates containing more than one electron donor site.

High Resolution Optical Spectroscopy of mer-[Cr(dpt)(Gly-Gly)]ClO₄

  • 최종하
    • Bulletin of the Korean Chemical Society
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    • v.20 no.4
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    • pp.436-440
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    • 1999
  • The highly resolved absorption spectra of mer-[Cr(dpt)(Gly-Gly)]ClO4·H2O [dpt = di(3-aminopropyl)amine, H2Gly-Gly = glycylglycine] have been measured between 13000 cm-1 and 50000 cm-1 temperatures down to 2 K. The vibrational intervals were extracted by recording emission and far-infrared spectra. The characteristic infrared bands in meridional isomer were discussed. The four-teen electronic origins due to spin-allowed and spin-forbidden transitions were assigned. With the use of this electronic transitions, a ligand field optimization based on the exact known ligand geometry have been performed to determine more detailed bonding properties of Gly-Gly and dpt ligands. It is confirmed that the peptide nitrogen of the Gly-Gly has a weak π-donor property toward chrornium(Ⅲ) ion.

A New Functional Model of Catechol Dioxygenases: Properties and Reactivity of [Fe(BLPA)DBC]$BPh_4$

  • Lim, Ji H.;Lee, Ho J.;이강봉;Jang, Ho G.
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1166-1172
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    • 1997
  • [FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

Second-order Nonlinear Optical Properties of Amorphous Molecules Based on 5-(4-Diethylamino-benzylidene)-1,3-dimethyl-pyrimidine-2,4,6-trione

  • Lee, Seung-Mook;Rhee, Bum-Ku;Lee, Sang-Ho;Lee, Chul-Joo;Park, Ki-Hong
    • Journal of Photoscience
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    • v.10 no.2
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    • pp.203-208
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    • 2003
  • Two coupled molecules were successfully synthesized by condensation of amine-donor-substituted barbituric acid derivativies as nonlinear optical chromophores. A flexible spacer of the alkyl chain with different lengths of carbon chains (5 and 6 carbons) was introduced between two chromophores, which prevented crystallization and aggregation of molecules. Two coupled molecules (B-Cn-B, n=5, 6) had glass-transition temperatures on a second heating around 81 and 76$^{\circ}C$ without melting points, respectively. To explore the linear optical properties, thin-films were prepared and examined by a photometry method using Nd:YVO$_4$ CW laser. Also, microscopic and macroscopic nonlinear optical properties were measured by Hyper-Rayleigh Scattering (HRS) and the Maker Fringes method using Nd:YAG ps pulse laser, respectively. In spite of the moderate hyperpolarizabilities of coupled molecules, the second order NLO coefficient (d$\_$33/) was larger than the conventional Disperse Red 1 doped PMMA polymeric system.

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Density Functional Theory Study on D-π-A-type Organic Dyes Containing Different Electron-Donors for Dye-Sensitized Solar Cells

  • Song, Jing;Xu, Jie
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3211-3217
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    • 2013
  • Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been employed to investigate the molecular structures and absorption spectra of three D-${\pi}$-A-type organic dyes (C1-1, D5 and TH208) containing identical ${\pi}$-spacers and electron acceptors, but different aromatic amine electron-donating groups (tetrahydroquinoline, triphenylamine and phenothiazine). The coplanar geometries indicate that the strong conjugation is formed in the dyes. The electronic structures suggest that the intramolecular charge transfer from the donor to the acceptor occurs, and the electron-donating ability of tetrahydroquinoline is stronger than those of triphenylamine and phenothiazine. The computed orbital energy levels of these dyes confirm that the electrons could be injected from the excited dyes to the semiconductor conduction band and the oxidized dyes could be reduced effectively by electrolyte. The TD-DFT results show that the CAM-B3LYP/6-31+G(d, p) is suitable for calculating the absorption spectra. The first absorption band for these dyes is assigned to the HOMO${\rightarrow}$LUMO and HOMO-1${\rightarrow}$LUMO transitions.